Compounds and the use thereof in metathesis reactions

ABSTRACT

The disclosure provides Group 6 complexes, which, in some embodiments, are useful for catalyzing olefin metathesis reactions. In some embodiments, the compounds are compounds of the following formula: 
     
       
         
         
             
             
         
       
     
     wherein:
         M is a Group 6 metal atom;   X is an oxygen atom, ═N—R 5 , ═N—N(R 5 )(R 5′ ) or ═N—O—R 5 , R 5  and R 5′  independently being various substituents, such as aryl or heteroaryl, each optionally substituted;   n is 0 or 1;   R z  is a neutral ligand;   R 1  is hydrogen or an organic substituent;   R 2  is an aryl or heteroaryl group, each optionally substituted;   R 3  is an anionic ligand; and   R 4  is an anionic ligand, such as a pyrrolide, a pyrazolide, an imidazolide, an indolide, an azaindolide, or an indazolide, each optionally substituted.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/988,199, filed Aug. 7, 2020, which is a continuation of U.S. patentapplication Ser. No. 16/167,250, filed Oct. 22, 2018, which is acontinuation of U.S. patent application Ser. No. 15/303,089, filed Oct.10, 2016, which is a National Stage Entry of International ApplicationNo. PCT/IB2015/000473, filed Apr. 9, 2015, which claims priority to U.S.Provisional Application No. 62/007,987, filed Jun. 5, 2014, and GreatBritain Patent Application No. GB1406591.6, filed Apr. 11, 2014, each ofwhich is incorporated herein by reference in its entirety.

TECHNICAL FIELD

Organometallic complexes and their use as catalyst compounds aregenerally disclosed herein. In some embodiments, the organometalliccomplexes disclosed herein catalyze a metathesis reaction betweenolefinically unsaturated compounds.

BACKGROUND

Alkene metathesis (olefin metathesis) is a reaction between alkenes orolefinic groups, in which formally alkylidene groups are exchangedbetween the alkenes or olefinic groups. Examples of metathesis reactionsinclude cross-metathesis, i.e. the reaction between two differentolefins forming a new olefin or new olefins, the ring opening metathesisof a cyclic diene, which may also proceed under polymerization, the ringclosing metathesis of a diene, the ethenolysis of an olefin having aninternal olefinic double bond to form olefins having a terminal olefinicdouble bonds, and the formation of internal olefin(s) from terminalolefin(s) via homo-metathesis reactions.

US 2011/007742 generally discloses catalysts and processes for theZ-selective formation of internal olefin(s) from terminal olefin(s) viahomo-metathesis reactions. The method includes reacting a first moleculehaving a terminal carbon-carbon double bond and a second, identicalmolecule via a homo-metathesis reaction to produce a product having aninternal carbon-carbon double bond, wherein the internal carbon-carbondouble bond of the product includes one carbon atom from the terminaldouble bond of the first molecule and one carbon atom from the terminaldouble bond of the second carbon atom, and wherein at least 60% of theinternal double bonds of the product are formed as the Z-isomer.

Further compounds based on molybdenum and tungsten and useful ascatalysts in metathesis reaction are disclosed in U.S. Pat. No.6,121,473, US 2008/0119678 and US 2011/0015430. Such catalysts usuallyare applied or have to be applied in a metathesis reaction in arelatively high molar amount with respect to the molar amount of olefinor olefins in order to achieve a sufficient degree of conversion of theolefin(s) used as starting material. A molar ratio up to 1:500 withrespect to the applied olefin(s) (molar ratio catalyst to olefin(s)) maybe necessary to achieve a conversion of 30% or more.

And because these catalysts may be relatively expensive to make, suchlow-conversion reactions may not be cost-effective at an industrialscale, and thus may lack industrial applicability. Further, suchcompounds may be more susceptible to degradation in the presence ofcertain atmospheric gases. Therefore, they may be difficult to use at alarger scale in an industrial process, where larger quantities may beneeded.

Therefore, there is a continuing need to develop organometalliccompounds that are stable and that provide relatively high conversion atlow catalyst concentrations.

SUMMARY

In a first aspect, the disclosure provides compounds of Formula (I)

wherein:

M is a Group 6 metal atom;

X is an oxygen atom, or ═N—R⁵, ═N—N(R⁵)(R^(5′)), or ═N—O—R⁵;

n is 0 or 1;

R^(z) is a neutral ligand;

R¹ is R¹¹ or -G¹-R¹¹;

R² is C₆₋₁₈ aryl or C₄₋₁₈ heteroaryl, each of which is optionallysubstituted one or more times by substituents selected independentlyfrom R⁶, wherein any two adjacent R⁶ optionally combine to form a ring,which is optionally substituted one or more times with substituentsselected independently from R^(x); or R² is -G¹⁰-R³³;

R³ is an anionic ligand, such as —OR⁷, —SR⁷, or —N(R⁷)(R^(7′));

R⁴ is pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl, 1H-1,2,3-triazol-1-yl,2H-1,2,3-triazol-2-yl, 1H-1,2,4-triazol-1-yl, 4H-1,2,4-triazol-4-yl,indol-1-yl, indazol-1-yl, azaindol-1-yl, —O—SiR²¹R²²R²³; or—O—CR²¹R²²R²³, wherein the pyrrolyl, pyrazolyl, imidazolyl, triazolyl,indazolyl, indazolyl, and azaindolyl groups are optionally substitutedone or more times with substituents selected independently from R⁸,wherein any two adjacent R⁸ optionally combine to form a ring, which isoptionally substituted one or more times with substituents selectedindependently from R^(x);

R⁵ is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl,C₂₋₂₀ heteroaryl, or —SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl,aryl, and heteroaryl groups are optionally substituted one or more timeswith substituents selected independently from R³¹, wherein any twoadjacent R³¹ optionally combine to form a ring, which is optionallysubstituted one or more times with substituents selected independentlyfrom R^(x); or R⁵ is -G⁵-R¹⁵;

R^(5′) is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀aryl, C₂₋₂₀ heteroaryl, or —SiR²¹R²²R²³, wherein the cycloalkyl,heterocyclyl, aryl, and heteroaryl groups are optionally substituted oneor more times with substituents selected independently from R³¹, whereinany two adjacent R³¹ optionally combine to form a ring, which isoptionally substituted one or more times with substituents selectedindependently from R^(x); or R^(5′) is -G⁵-R¹⁵;

R⁶ is R¹⁶ or -G⁶-R¹⁶;

R⁷ is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl,C₂₋₂₀ heteroaryl, —C(O)—R²¹, —C(O)—NR²¹R²², —CR²¹R²²R²³, or—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, and heteroarylgroups are optionally substituted one or more times with substituentsselected independently from R³¹, wherein any two adjacent R³¹ optionallycombine to form a ring, which is optionally substituted one or moretimes with substituents selected independently from R^(x); or R⁷ is-G⁷-R¹⁷;

R^(7′) is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀aryl, C₂₋₂₀ heteroaryl, —C(O)—R²¹, —C(O)—NR²¹R²², —CR²¹R²²R²³, or—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, and heteroarylgroups are optionally substituted one or more times with substituentsselected independently from R³¹, wherein any two adjacent R³¹ optionallycombine to form a ring, which is optionally substituted one or moretimes with substituents selected independently from R^(x); or R^(7′) is-G⁷-R¹⁷;

R⁸ is R¹⁸ or -G⁸-R¹⁸;

G¹, G⁵, G⁶, G⁷, and G⁸ are independently C₁₋₁₂ alkylene, C₂₋₁₂alkenylene, or C₂₋₁₂ alkynylene, each of which is optionally substitutedone or more times with substituents selected independently from R³²;

R¹¹, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are independently a hydrogen atom, a halogenatom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀heteroaryl, —CN, —O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹,—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²²,—C(O)—NR²¹R²², —N(R²¹)—C(O)—R²², —N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²²,—N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²², —N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or—O—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R³¹, wherein any two adjacentR³¹ optionally combine to form a ring, which is optionally substitutedone or more times with substituents selected independently from R^(x);

R²¹, R²², and R²³ are independently R²⁸ or -G⁹-R²⁹, or when two of R²¹,R²², and R²³ are attached to the same atom, they optionally combine toform a C₃₋₂₀ carbocyclic ring or a C₂₋₂₀ heterocyclic ring, each ofwhich is optionally substituted one or more times with substituentsselected independently from R^(x);

G⁹ is C₁₋₁₂ alkylene, C₂₋₁₂ alkenylene, or C₂₋₁₂ alkynylene, each ofwhich is optionally substituted one or more times with substituentsselected independently from R^(y);

R²⁸ is C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, or C₂₋₂₀heteroaryl, each of which is optionally substituted one or more timeswith substituents selected independently from R^(x); or R²⁸ is ahydrogen atom;

R²⁹ is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀aryl, or C₂₋₂₀ heteroaryl, wherein the cycloalkyl, heterocyclyl, aryl,and heteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R^(x);

R³¹ is a halogen atom, C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₁₂cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀ heteroaryl, —CN,—O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹, —C(O)—R²¹, —O—C(O)—R²¹,—O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²², —C(O)—NR²¹R²², —N(R²¹)—C(O)—R²²,—N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²², —N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²²,—N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or —O—SiR²¹R²²R²³, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R⁴¹, wherein any two adjacent R⁴¹ optionally combine to form aring, which is optionally substituted one or more times withsubstituents selected independently from R^(x), and wherein the alkyl,alkenyl, and alkynyl groups are optionally substituted one or more timeswith substituents selected independently from R⁴²;

R³² is a halogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl,C₂₋₂₀ heteroaryl, —CN, —O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹,—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²²,—C(O)—NR²¹R²², —N(R²¹)—C(O)—R²², —N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²²,—N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²², —N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or—O—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R⁴¹, wherein any two adjacentR⁴¹ optionally combine to form a ring, which is optionally substitutedone or more times with substituents selected independently from R^(x);

G¹⁰ is —O—, —S—, —Se—, —C(R²¹)(R²²)—, —Si(R²¹)(R²²)—, or —N(R²¹)—,wherein the R²¹ of the —NR²¹— group optionally combines with R³³ to forma nitrogen-containing heterocyclic ring, which is optionally substitutedone or more times with substituents selected independently from R^(x),and wherein any carbon atoms of the nitrogen-containing heterocyclicring are optionally oxidized to form a carbonyl group;

R³³ is C₂₋₂₀ heterocyclyl or C₂₋₂₀ heteroaryl, each of which isoptionally substituted one or more times by substituents selectedindependently from R⁴¹, wherein any two adjacent R⁴¹ optionally combineto form a ring, which is optionally substituted one or more times withsubstituents selected independently from R^(x); or R³³ is C₂₋₂₀heteroalkyl, which is optionally substituted one or more times bysubstituents selected independently from R⁴²; or R³³ is —C(O)—R⁴³.

R⁴¹ is a halogen atom, C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₁₂cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀ heteroaryl, —CN,—O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹, —C(O)—R²¹, —O—C(O)—R²¹,—O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²², —C(O)—NR²¹R²², —N(R²¹)—C(O)—R²²,—N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²², —N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²²,—N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or —O—SiR²¹R²²R²³, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R^(x), and wherein the alkyl, alkenyl, and alkynyl groups areoptionally substituted one or more times with substituents selectedindependently from R^(y);

R⁴² is a halogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl,C₂₋₂₀ heteroaryl, —CN, —O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹,—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²²,—C(O)—NR²¹R²², —N(R²¹)—C(O)—R²², —N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²²,—N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²², —N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or—O—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R^(x);

R⁴³ is C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₁₂ cycloalkyl,C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, or C₂₋₂₀ heteroaryl, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R^(x), and wherein the alkyl, alkenyl, and alkynyl groups areoptionally substituted one or more times with substituents selectedindependently from R^(y);

R^(x) is a halogen atom, C₁₋₆ alkyl, C₃₋₁₀ cycloalkyl, phenyl, —CN, —OH,—O(C₁₋₆ alkyl), —SO₂(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆alkyl)₂, —C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆alkyl)₃, or —O—Si(C₁₋₆ alkyl)₃;

R^(y) is a halogen atom, C₃₋₁₀ cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆alkyl), —SO₂(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂,—C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆ alkyl)₃, or—O—Si(C₁₋₆ alkyl)₃; and

w is 0, 1, or 2;

wherein R¹ and R² optionally combine to form a ring, and R² and R³optionally combine to form a ring, and R³ and R⁴ optionally combine toform a ring;

provided that if R³ is —O—R⁷, R⁷ is -G⁷-R¹⁷, G⁷ is alkylene, and R¹⁷ isa hydrogen atom or a halogen atom, then R⁴ is not —O—CR²¹R²²R²³.

In a second aspect, the disclosure provides compounds of Formula (II)

wherein:

M is a molybdenum atom or a tungsten atom;

R¹⁰¹ is aryl, heteroaryl, alkyl, or cycloalkyl, each of which isoptionally substituted;

R¹⁰² is pyrrolyl, imidazolyl, indolyl, pyrazolyl, azaindolyl, orindazolyl, each of which is optionally substituted; or R¹⁰² is—O—Si(phenyl)₃ when R¹⁰³ is —Si(phenyl)₃, the phenyl groups beingoptionally substituted;

R¹⁰³ is C₁₋₆ alkyl, C₁₋₆ heteroalkyl, aryl, or heteroaryl, each of whichis optionally substituted; or R¹⁰³ is tert-butyl, —C(CH₃)₂(CF₃),—C(CF₃)₃, or —C(CF₃)₂-(phenyl); or R¹⁰³ is —Si(phenyl)₃ when R¹⁰² is—O—Si(phenyl)₃, the phenyl groups being optionally substituted;

R¹⁰⁴ is a hydrogen atom, C₁₋₆ alkyl, or alkoxy;

R¹⁰⁵ is a hydrogen atom, —O—(C₁₋₆ alkyl), —CH₂—O—(C₁₋₆ alkyl),heteroalkoxy, or —N(C₁₋₆ alkyl)₂;

R¹⁰⁶ and R¹⁰⁷ are independently a hydrogen atom, C₁₋₆ alkyl, C₁₋₆alkoxy, a halogen atom, —NO₂, amides, or sulfonamides.

In a third aspect, the disclosure provides methods of carrying out ametathesis reaction, including: providing a first compound having one ormore carbon-carbon double bonds; and reacting the first compound via ametathesis reaction in the presence of a metathesis catalyst, such as acompound of the first or second aspects disclosed herein. In someembodiments, the first compound has two or more carbon-carbon doublebonds. In some such embodiments, the metathesis reaction is aring-closing metathesis reaction between two of the two or morecarbon-carbon double bonds of the first compound.

In a fourth aspect, the disclosure provides methods of carrying out ametathesis reaction, including: providing a first compound having one ormore carbon-carbon double bond and a second compound having one or morecarbon-carbon double bonds; and reacting the first compound and thesecond compound via a metathesis reaction in the presence of ametathesis reaction, such as a compound of the first or second aspectsdisclosed herein. In some embodiments, the first compound and the secondcompound are the same compound. In some other embodiments, the firstcompound and the second compound are not the same. In some suchembodiments, the first compound is an internal olefin, such as a naturaloil. In some embodiments, the second compound is a short-chain alkene,such as ethylene. In some such embodiments, the metathesis reactionyields an amount of 9-decenoic acid or an ester or carboxylate saltthereof.

Further aspects and embodiments are disclosed in greater detail in theforegoing detailed description, examples, and claims, and in anydrawings.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of theinventions disclosed herein. No particular embodiment is intended todefine the scope of the invention. Rather, the embodiments providenon-limiting examples of various compositions, and methods that areincluded within the scope of the claimed inventions. The description isto be read from the perspective of one of ordinary skill in the art.Therefore, information that is well known to the ordinarily skilledartisan is not necessarily included.

Definitions

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any way. Nor dothese phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “natural oil,” “natural feedstock,” or “natural oilfeedstock” refer to oils derived from plants or animal sources. Theseterms include natural oil derivatives, unless otherwise indicated. Theterms also include modified plant or animal sources (e.g., geneticallymodified plant or animal sources), unless indicated otherwise. Examplesof natural oils include, but are not limited to, vegetable oils, algaeoils, fish oils, animal fats, tall oils, derivatives of these oils,combinations of any of these oils, and the like. Representativenon-limiting examples of vegetable oils include rapeseed oil (canolaoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, and castor oil. Representativenon-limiting examples of animal fats include lard, tallow, poultry fat,yellow grease, and fish oil. Tall oils are by-products of wood pulpmanufacture. In some embodiments, the natural oil or natural oilfeedstock comprises one or more unsaturated glycerides (e.g.,unsaturated triglycerides). In some such embodiments, the natural oilfeedstock comprises at least 50% by weight, or at least 60% by weight,or at least 70% by weight, or at least 80% by weight, or at least 90% byweight, or at least 95% by weight, or at least 97% by weight, or atleast 99% by weight of one or more unsaturated triglycerides, based onthe total weight of the natural oil feedstock.

As used herein, “natural oil derivatives” refers to the compounds ormixtures of compounds derived from a natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial, selective, or full),isomerization, oxidation, and reduction. Representative non-limitingexamples of natural oil derivatives include gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl ester (e.g. non-limiting examples such as2-ethylhexyl ester), hydroxy substituted variations thereof of thenatural oil. For example, the natural oil derivative may be a fatty acidmethyl ester (“FAME”) derived from the glyceride of the natural oil. Insome embodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

As used herein, “metathesis catalyst” includes any catalyst or catalystsystem that catalyzes an olefin metathesis reaction.

As used herein, “metathesis,” “metathesize,” or “metathesizing” refer tothe reacting of a feedstock in the presence of a metathesis catalyst toform a “metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “hydrocarbon” refers to an organic group composed ofcarbon and hydrogen, which can be saturated or unsaturated, and caninclude aromatic groups. The term “hydrocarbyl” refers to a monovalentor polyvalent hydrocarbon moiety.

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin” or an “alpha-olefin,” while an olefin having anon-terminal carbon-carbon double bond can be referred to as an“internal olefin.” In some embodiments, the alpha-olefin is a terminalalkene, which is an alkene (as defined below) having a terminalcarbon-carbon double bond. Additional carbon-carbon double bonds can bepresent.

The number of carbon atoms in any group or compound can be representedby the terms: “C_(z)”, which refers to a group of compound having zcarbon atoms, and “C_(x-y)” refers to a group or compound containingfrom x to y, inclusive, carbon atoms. For example, “C₁₋₆ alkyl”represents an alkyl group (as defined below) having from 1 to 6 carbonatoms and, for example, includes, but is not limited to, methyl, ethyl,n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl,isopentyl, n-pentyl, neopentyl, and n-hexyl. As a further example, a“C₄₋₁₀ alkene” refers to an alkene molecule having from 4 to 10 carbonatoms, and, for example, includes, but is not limited to, 1-butene,2-butene, isobutene, 1-pentene, 1-hexene, 3-hexene, 1-heptene,3-heptene, 1-octene, 4-octene, 1-nonene, 4-nonene, and 1-decene.

As used herein, the term “low-molecular-weight olefin” may refer to anyone or combination of unsaturated straight, branched, or cyclichydrocarbons in the C₂₋₁₄ range. Such compounds include alpha-olefins,wherein the unsaturated carbon-carbon bond is present at one end of thecompound. They may also include dienes or trienes. Low-molecular-weightolefins may also include internal olefins or “low-molecular-weightinternal olefins.” In certain embodiments, the low-molecular-weightinternal olefin is in the C₂₋₆ range. Examples of low-molecular-weightolefins in the C₂₋₆ range include, but are not limited to: ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. Non-limiting examples oflow-molecular-weight olefins in the C₇₋₉ range include 1,4-heptadiene,1-heptene, 3,6-nonadiene, 3-nonene, 1,4,7-octatriene. Otherlow-molecular-weight olefins include styrene and vinyl cyclohexane.Olefins in the C₂₋₁₀ range can also be referred to as “short-chainolefins,” which can be either branched or unbranched. In someembodiments, it may be preferable to use a mixture of linear andbranched C₄ olefins (i.e., combinations of: 1-butene, 2-butene, and/orisobutene).

In some instances, the olefin can be an “alkene,” which refers to astraight- or branched-chain non-aromatic hydrocarbon having 2 to 30carbon atoms and one or more carbon-carbon double bonds, which may beoptionally substituted, as herein described, with multiple degrees ofsubstitution being allowed. A “monounsaturated alkene” refers to analkene having one carbon-carbon double bond, while a “polyunsaturatedalkene” refers to an alkene having two or more carbon-carbon doublebonds. A “lower alkene,” as used herein, refers to an alkene having from2 to 10 carbon atoms.

As used herein, “ester” or “esters” refer to compounds having thegeneral formula: R—COO—R′, wherein R and R′ denote any organic group(such as alkyl, aryl, or silyl groups) including those bearingheteroatom-containing substituent groups. In certain embodiments, R andR′ denote alkyl, alkenyl, aryl, or alcohol groups. In certainembodiments, the term “esters” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. In certain embodiments, the esters may beesters of glycerol, which is a trihydric alcohol. The term “glyceride”can refer to esters where one, two, or three of the —OH groups of theglycerol have been esterified.

It is noted that an olefin may also comprise an ester, and an ester mayalso comprise an olefin, if the R or R′ group in the general formulaR—COO—R′ contains an unsaturated carbon-carbon double bond. Suchcompounds can be referred to as “unsaturated esters” or “olefin ester”or “olefinic ester compounds.” Further, a “terminal olefinic estercompound” may refer to an ester compound where R has an olefinpositioned at the end of the chain. An “internal olefin ester” may referto an ester compound where R has an olefin positioned at an internallocation on the chain. Additionally, the term “terminal olefin” mayrefer to an ester or an acid thereof where R′ denotes hydrogen or anyorganic compound (such as an alkyl, aryl, or silyl group) and R has anolefin positioned at the end of the chain, and the term “internalolefin” may refer to an ester or an acid thereof where R′ denoteshydrogen or any organic compound (such as an alkyl, aryl, or silylgroup) and R has an olefin positioned at an internal location on thechain.

As used herein, the term “unsaturated glyceride” refers to mono-, di-,or tri-esters of glycerol, which include one or more carbon-carbondouble bonds. For example, in some embodiments, the “unsaturatedglyceride” can be represented by the formula R—O—CH₂—CH(OR′)—CH₂(OR″),wherein at least one of R, R′, and R″ is a substituted or unsubstitutedalkenyl group. In some embodiments, the other group(s) are hydrogen,alkyl, or alkenyl. Examples of unsaturated triglycerides include certainunsaturated fats derived from natural oils.

As used herein, “alkyl” refers to a straight or branched chain saturatedhydrocarbon having 1 to 30 carbon atoms, which may be optionallysubstituted, as herein further described, with multiple degrees ofsubstitution being allowed. Examples of “alkyl,” as used herein,include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl,neopentyl, n-hexyl, and 2-ethylhexyl. The number of carbon atoms in analkyl group is represented by the phrase “C_(x-y) alkyl,” which refersto an alkyl group, as herein defined, containing from x to y, inclusive,carbon atoms. Thus, “C₁₋₆ alkyl” represents an alkyl chain having from 1to 6 carbon atoms and, for example, includes, but is not limited to,methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl,tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. In someinstances, the “alkyl” group can be divalent, in which case the groupcan alternatively be referred to as an “alkylene” group. Also, in someinstances, one or more of the carbon atoms in the alkyl or alkylenegroup can be replaced by a heteroatom (e.g., selected independently fromnitrogen, oxygen, silicon, selenium, or sulfur, including N-oxides,sulfur oxides, and sulfur dioxides, where feasible), and is referred toas a “heteroalkyl” or a “heteroalkylene” group, respectively.

As used herein, “alkenyl” refers to a straight or branched chainnon-aromatic hydrocarbon having 2 to 30 carbon atoms and having one ormore carbon-carbon double bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkenyl,” as used herein, include, but are notlimited to, ethenyl, 2-propenyl, 2-butenyl, and 3-butenyl. The number ofcarbon atoms in an alkenyl group is represented by the phrase “C_(x-y)alkenyl,” which refers to an alkenyl group, as herein defined,containing from x to y, inclusive, carbon atoms. Thus, “C₂₋₆ alkenyl”represents an alkenyl chain having from 2 to 6 carbon atoms and, forexample, includes, but is not limited to, ethenyl, 2-propenyl,2-butenyl, 3-butenyl, and 2-hexenyl. In some instances, the “alkenyl”group can be divalent, in which case the group can alternatively bereferred to as an “alkenylene” group.

As used herein, “alkynyl” refers to a straight or branched chainnon-aromatic hydrocarbon having 2 to 30 carbon atoms and having one ormore carbon-carbon triple bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkynyl,” as used herein, include, but are notlimited to, ethynyl, 2-propynyl, 2-butynyl, and 3-butynyl. The number ofcarbon atoms in an alkynyl group is represented by the phrase “C_(x-y)alkynyl,” which refers to an alkynyl group, as herein defined,containing from x to y, inclusive, carbon atoms. Thus, “C₂₋₆ alkynyl”represents an alkynyl chain having from 2 to 6 carbon atoms and, forexample, includes, but is not limited to, ethynyl, 2-propynyl,2-butynyl, 3-butynyl, and 2-hexynyl. In some instances, the “alkynyl”group can be divalent, in which case the group can alternatively bereferred to as an “alkynylene” group.

As used herein, “cycloalkyl” refers to an aliphatic saturated orunsaturated hydrocarbon ring system having 1 to 20 carbon atoms, whichmay be optionally substituted, as herein further described, withmultiple degrees of substitution being allowed. Examples of“cycloalkyl,” as used herein, include, but are not limited to,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl,cycloheptyl, cyclooctyl, adamantyl, and the like. The number of carbonatoms in a cycloalkyl group is represented by the phrase “C_(x-y)cycloalkyl,” which refers to a cycloalkyl group, as herein defined,containing from x to y, inclusive, carbon atoms. Thus, “C₃₋₁₀cycloalkyl” represents a cycloalkyl having from 3 to 10 carbon atomsand, for example, includes, but is not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl,cyclooctyl, and adamantyl. In some instances, the “cycloalkyl” group canbe divalent, in which case the group can alternatively be referred to asa “cycloalkylene” group. Cycloalkyl and cycloalkylene groups can also bereferred to herein as “carbocyclic rings.” Also, in some instances, oneor more of the carbon atoms in the cycloalkyl or cycloalkylene group canbe replaced by a heteroatom (e.g., selected independently from nitrogen,oxygen, silicon, or sulfur, including N-oxides, sulfur oxides, andsulfur dioxides, where feasible), and is referred to as a “heterocyclyl”or “heterocyclylene” group, respectively. The term “heterocyclic ring”can also be used interchangeable with either of these terms. In someembodiments, the cycloalkyl and heterocyclyl groups are fully saturated.In some other embodiments, the cycloalkyl and heterocyclyl groups cancontain one or more carbon-carbon double bonds.

As used herein, “aryl” refers to a 6- to 30-membered cyclic, aromatichydrocarbon, which may be optionally substituted as herein furtherdescribed, with multiple degrees of substitution being allowed. Examplesof “aryl” groups, as used herein include, but are not limited to, phenyland naphthyl. As used herein, the term “aryl” also includes ring systemsin which a phenyl or naphthyl group is optionally fused with one tothree non-aromatic, saturated or unsaturated, carbocyclic rings. Forexample, “aryl” would include ring systems such as indene, withattachment possible to either the aromatic or the non-aromatic ring(s).In some embodiments, the aryl group, as used herein, is selected fromthe group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each ofwhich is optionally substituted, as further described herein. Further,in some embodiments, the “aryl” group refers to a ring system thatincludes only aromatic rings.

As used herein, the term “heteroaryl” refers to a 5- to 30-memberedmono- or polycyclic ring system, which contains at least one aromaticring and also contains one or more heteroatoms, such as oxygen,nitrogen, silicon, or sulfur. Such “heteroaryl” groups may be optionallysubstituted as herein further described, with multiple degrees ofsubstitution being allowed. In a polycyclic “heteroaryl” group thatcontains at least one aromatic ring and at least one non-aromatic ring,the aromatic ring(s) need not contain a heteroatom. Thus, for example,“heteroaryl,” as used herein, would include indolinyl. Further, thepoint of attachment may be to any ring within the ring system withoutregard to whether the ring containing the attachment point is aromaticor contains a heteroatom. Thus, for example, “heteroaryl,” as usedherein, would include indolin-1-yl, indolin-3-yl, and indolin-5-yl.Examples of heteroatoms include nitrogen, oxygen, or sulfur atoms,including N-oxides, sulfur oxides, and sulfur dioxides, where feasible.Examples of “heteroaryl” groups, as used herein include, but are notlimited to, furyl, thiophenyl, pyrrolyl, oxazolyl, thiazolyl,imidazolyl, isoxazolyl, isothiazolyl, 1,2,4-triazolyl, pyrazolyl,pyridinyl, pyridazinyl, pyrimidinyl, indolyl, isoindolyl,benzo[b]thiophenyl, benzimidazolyl, benzothiazolyl, pteridinyl, andphenazinyl, where attachment can occur at any point on said rings, aslong as attachment is chemically feasible. Thus, for example,“thiazolyl” refers to thiazol-2-yl, thiazol-4-yl, and thiaz-5-yl.

As used herein, “alkoxy” or “alkyloxy” refer to —OR, where R is an alkylgroup (as defined above). The number of carbon atoms in an alkyl groupis represented by the phrase “C_(x-y) alkoxy,” which refers to an alkoxygroup having an alkyl group, as herein defined, having from x to y,inclusive, carbon atoms.

As used herein, “halogen atom” or “halo” refers to a fluorine, chlorine,bromine, or iodine atom. In some embodiments, the terms refer to afluorine or chlorine atom. As used herein, “haloalkyl” or “haloalkoxy”refer to alkyl or alkoxy groups, respectively, (as defined above)substituted by one or more times by halogen atoms.

The term “Group 6 metal atom” refers to a chromium, molybdenum,tungsten, or seaborgium atom. In some embodiments, the term refers to achromium, molybdenum, or tungsten atom. In some further embodiments, theterm refers to a tungsten or molybdenum atom.

The term “azaindole” or its variants refers to 4-azaindole, 5-azaindole,6-azaindole, and 7-azaindole, collectively. In some embodiments, theterm refers to 7-azaindole. In some other embodiments, the term refersto 6-azaindole. In some other embodiments, the term refers to5-azaindole. In some other embodiments, the term refers to 4-azaindole.

The term “ring” refers to any ring system, including bicyclic andtricyclic ring systems, and fused ring systems. In some instances, thephrase “wherein any two adjacent R (i.e., substituents) optionallycombine to form a ring” refers to two adjacent substituents bondingtogether to form a ring system that at least includes bond(s) betweenthe two substituted atoms. For example, substituents at the 3- and4-positions on a phenyl ring optionally combine to form a four-memberedcarbocyclic ring (i.e., a 5,6,7,8-tetrahydronaphthyl group). “Adjacent”substituents need not be immediately adjacent, as long as the resultingring formation yields a stable moiety.

As used herein, “substituted” refers to substitution of one or morehydrogen atoms of the designated moiety with the named non-hydrogensubstituent or substituents, multiple degrees of substitution beingallowed unless otherwise stated, provided that the substitution resultsin a stable or chemically feasible compound. A stable compound orchemically feasible compound is one in which the chemical structure isnot substantially altered when kept at a temperature from about −80° C.to about +40° C., in the absence of moisture or other chemicallyreactive conditions, for at least a week, or a compound which maintainsits integrity long enough to be useful for catalyzing a reaction betweentwo olefins. As used herein, the phrases “substituted with one or more .. . ” or “substituted one or more times . . . ” refer to a number ofsubstituents that equals from one to the maximum number of substituentspossible based on the number of available bonding sites, provided thatthe above conditions of stability and chemical feasibility are met.Further, phrases such as “substituted one or more times by substituentsselected independently from R” means that the identity of the one ormore substituents are, for each point of substitution, to be selectedfrom the list of substituents recited for R. In this instance, the term“independently” implies that, in cases where two or more substitutionsoccur, the identity of one substituent selected from R is unaffected bythe identity of other substituents selected from R.

As used herein, the term “anionic ligand” refers to a ligand that isanionic, with respect to charge, when formally removed from the metal inits closed-shell electronic state. In some embodiments, the anionicligand has a −1 charge when formally removed from the metal in itsclosed-shell electronic state.

As used herein, the term “neutral ligand” refers to a ligand that isneutral, with respect to charge, when formally removed from the metal inits closed-shell electronic state.

As used herein, “yield” refers to the amount of reaction product formedin a reaction. When expressed with units of percent (%), the term yieldrefers to the amount of reaction product actually formed, as apercentage of the amount of reaction product that would be formed if allof the limiting reactant were converted into the product.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compounds or compositions. The two or morecompositions need not have the same physical state; thus, solids can be“mixed” with liquids, e.g., to form a slurry, suspension, or solution.Further, these terms do not require any degree of homogeneity oruniformity of composition. This, such “mixtures” can be homogeneous orheterogeneous, or can be uniform or non-uniform. Further, the terms donot require the use of any particular equipment to carry out the mixing,such as an industrial mixer.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (-) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

Unless otherwise indicated, when various terms are combined to name asubstituent, the earlier named feature is farther from the point ofattachment. For example, the term “alkyloxymethyl” refers to asubstituent having the following structure: —CH₂—O—(C₁₋₆ alkyl).

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Group 6 Metal Complexes

In at least one aspect, the disclosure provides Group 6 metal complexes,which, among other uses, are suitable for use as catalyst compounds,e.g., catalysts for olefin metathesis reactions. In at least one aspect,the disclosure provides compounds of Formula (I)

wherein:

M is a Group 6 metal atom;

X is an oxygen atom, or ═N—R⁵, ═N—N(R⁵)(R^(5′)), or ═N—O—R⁵;

n is 0 or 1;

R^(z) is a neutral ligand;

R¹ is R¹¹ or -G¹-R¹¹;

R² is C₆₋₁₈ aryl or C₄₋₁₈ heteroaryl, each of which is optionallysubstituted one or more times by substituents selected independentlyfrom R⁶, wherein any two adjacent R⁶ optionally combine to form a ring,which is optionally substituted one or more times with substituentsselected independently from R^(x); or R² is -G¹⁰-R³³;

R³ is an anionic ligand, such as —OR⁷, —SR⁷, or —N(R⁷)(R^(7′));

R⁴ is pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl, 1H-1,2,3-triazol-1-yl,2H-1,2,3-triazol-2-yl, 1H-1,2,4-triazol-1-yl, 4H-1,2,4-triazol-4-yl,indol-1-yl, indazol-1-yl, azaindol-1-yl, —O—SiR²¹R²²R²³; or—O—CR²¹R²²R²³, wherein the pyrrolyl, pyrazolyl, imidazolyl, triazolyl,indolyl, indazolyl, and azaindolyl groups are optionally substituted oneor more times with substituents selected independently from R⁸, whereinany two adjacent R⁸ optionally combine to form a ring, which isoptionally substituted one or more times with substituents selectedindependently from R^(x);

R⁵ is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl,C₂₋₂₀ heteroaryl, or —SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl,aryl, and heteroaryl groups are optionally substituted one or more timeswith substituents selected independently from R³¹, wherein any twoadjacent R³¹ optionally combine to form a ring, which is optionallysubstituted one or more times with substituents selected independentlyfrom R^(x); or R⁵ is -G⁵-R¹⁵;

R^(5′) is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀aryl, C₂₋₂₀ heteroaryl, or —SiR²¹R²²R²³, wherein the cycloalkyl,heterocyclyl, aryl, and heteroaryl groups are optionally substituted oneor more times with substituents selected independently from R³¹, whereinany two adjacent R³¹ optionally combine to form a ring, which isoptionally substituted one or more times with substituents selectedindependently from R^(x); or R^(5′) is -G⁵-R¹⁵;

R⁶ is R¹⁶ or -G⁶-R¹⁶;

R⁷ is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl,C₂₋₂₀ heteroaryl, —C(O)—R²¹, —C(O)—NR²¹R²², —CR²¹R²²R²³, or—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, and heteroarylgroups are optionally substituted one or more times with substituentsselected independently from R³¹, wherein any two adjacent R³¹ optionallycombine to form a ring, which is optionally substituted one or moretimes with substituents selected independently from R^(x); or R⁷ is-G⁷-R¹⁷;

R^(7′) is a hydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀aryl, C₂₋₂₀ heteroaryl, —C(O)—R²¹, —C(O)—NR²¹R²², —CR²¹R²²R²³, or—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, and heteroarylgroups are optionally substituted one or more times with substituentsselected independently from R³¹, wherein any two adjacent R³¹ optionallycombine to form a ring, which is optionally substituted one or moretimes with substituents selected independently from R^(x); or R^(7′) is-G⁷-R¹⁷;

R⁸ is R¹⁸ or -G⁸-R¹⁸;

G¹, G⁵, G⁶, G⁷, and G⁸ are independently C₁₋₁₂ alkylene, C₂₋₁₂alkenylene, or C₂₋₁₂ alkynylene, each of which is optionally substitutedone or more times with substituents selected independently from R³²;

R¹¹, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are independently a hydrogen atom, a halogenatom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀heteroaryl, —CN, —O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹,—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²²,—C(O)—NR²¹R²², —N(R²¹)—C(O)—R²², —N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²²,—N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²², —N(R²¹)—SO₂—R²², —SiR²¹R²²R²³,—O—SiR²¹R²²R²³, or —NO₂, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R³¹, wherein any two adjacentR³¹ optionally combine to form a ring, which is optionally substitutedone or more times with substituents selected independently from R^(x);

R²¹, R²², and R²³ are independently R²⁸ or -G⁹-R²⁹, or when two of R²¹,R²², and R²³ are attached to the same atom, they optionally combine toform a C₃₋₂₀ carbocyclic ring or a C₂₋₂₀ heterocyclic ring, each ofwhich is optionally substituted one or more times with substituentsselected independently from R^(x);

G⁹ is C₁₋₁₂ alkylene, C₂₋₁₂ alkenylene, or C₂₋₁₂ alkynylene, each ofwhich is optionally substituted one or more times with substituentsselected independently from R^(y);

R²⁸ is C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, or C₂₋₂₀heteroaryl, each of which is optionally substituted one or more timeswith substituents selected independently from R^(x); or R²⁸ is ahydrogen atom;

R²⁹ is a hydrogen atom, a halogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂heterocyclyl, C₆₋₂₀ aryl, or C₂₋₂₀ heteroaryl, wherein the cycloalkyl,heterocyclyl, aryl, and heteroaryl groups are optionally substituted oneor more times with substituents selected independently from R^(x);

R³¹ is a halogen atom, C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₁₂cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀ heteroaryl, —CN,—O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹, —C(O)—R²¹, —O—C(O)—R²¹,—O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²², —C(O)—NR²¹R²², —N(R²¹)—C(O)—R²²,—N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²², —N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²²,—N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, —O—SiR²¹R²²R²³, or —NO₂, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R⁴¹, wherein any two adjacent R⁴¹ optionally combine to form aring, which is optionally substituted one or more times withsubstituents selected independently from R^(x), and wherein the alkyl,alkenyl, and alkynyl groups are optionally substituted one or more timeswith substituents selected independently from R⁴²;

R³² is a halogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl,C₂₋₂₀ heteroaryl, —CN, —O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹,—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²²,—C(O)—NR²¹R²², —N(R²¹)—C(O)—R²², —N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²²,—N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²², —N(R²¹)—SO₂—R²², —SiR²¹R²²R²³,—O—SiR²¹R²²R²³, or —NO₂, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R⁴¹, wherein any two adjacentR⁴¹ optionally combine to form a ring, which is optionally substitutedone or more times with substituents selected independently from R^(x);

G¹⁰ is —O—, —S—, —Se—, —C(R²¹)(R²²)—, —Si(R²¹)(R²²)—, or —N(R²¹)—,wherein the R²¹ of the —NR²¹— group optionally combines with R³³ to forma nitrogen-containing heterocyclic ring, which is optionally substitutedone or more times with substituents selected independently from R^(x),and wherein any carbon atoms of the nitrogen-containing heterocyclicring are optionally oxidized to form a carbonyl group;

R³³ is C₂₋₂₀ heterocyclyl or C₂₋₂₀ heteroaryl, each of which isoptionally substituted one or more times by substituents selectedindependently from R⁴¹, wherein any two adjacent R⁴¹ optionally combineto form a ring, which is optionally substituted one or more times withsubstituents selected independently from R^(x); or R³³ is C₂₋₂₀heteroalkyl, which is optionally substituted one or more times bysubstituents selected independently from R⁴²; or R³³ is —C(O)—R⁴³.

R⁴¹ is a halogen atom, C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₁₂cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀ heteroaryl, —CN,—O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹, —C(O)—R²¹, —O—C(O)—R²¹,—O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²², —C(O)—NR²¹R²², —N(R²¹)—C(O)—R²²,—N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²², —N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²²,—N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, —O—SiR²¹R²²R²³, or —NO₂, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R^(x), and wherein the alkyl, alkenyl, and alkynyl groups areoptionally substituted one or more times with substituents selectedindependently from R^(y);

R⁴² is a halogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl,C₂₋₂₀ heteroaryl, —CN, —O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹,—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²²,—C(O)—NR²¹R²², —N(R²¹)—C(O)—R²², —N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²²,—N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²², —N(R²¹)—SO₂—R²², —SiR²¹R²²R²³,—O—SiR²¹R²²R²³, or —NO₂, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R^(x);

R⁴³ is C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₁₂ cycloalkyl,C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, or C₂₋₂₀ heteroaryl, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R^(x), and wherein the alkyl, alkenyl, and alkynyl groups areoptionally substituted one or more times with substituents selectedindependently from R^(y);

R^(x) is a halogen atom, C₁₋₆ alkyl, C₃₋₁₀ cycloalkyl, phenyl, —CN, —OH,—O(C₁₋₆ alkyl), —SO₂(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆alkyl)₂, —C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆alkyl)₃, —O—Si(C₁₋₆ alkyl)₃, or —NO₂;

R^(y) is a halogen atom, C₃₋₁₀ cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆alkyl), —SO₂(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂,—C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆ alkyl)₃,—O—Si(C₁₋₆ alkyl)₃, or —NO₂; and

w is 0, 1, or 2;

wherein R¹ and R² optionally combine to form a ring, and R² and R³optionally combine to form a ring, and R³ and R⁴ optionally combine toform a ring;

provided that if R³ is —O—R⁷, R⁷ is -G⁷-R¹⁷, G⁷ is alkylene, and R¹⁷ isa hydrogen atom or a halogen atom, then R⁴ is not —O—CR²¹R²²R²³.

In some embodiments of any of the aforementioned embodiments, R⁷ is ahydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀heteroaryl, —C(O)—R²¹, —C(O)—NR²¹R²², —SiR²¹R²²R²³, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R³¹, wherein any two adjacent R³¹ optionally combine to form aring, which is optionally substituted one or more times withsubstituents selected independently from R^(x); or R⁷ is -G⁷-R¹⁷;

In some embodiments of any of the aforementioned embodiments, R²⁹ is ahydrogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, orC₂₋₂₀ heteroaryl, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R^(x).

In some embodiments of any of the aforementioned embodiments, G¹⁰ is—O—, —S—, —Se—, —C(R²¹)(R²²)—, —Si(R²¹)(R²²)—, or —N(R²¹)—.

In some embodiments of any of the aforementioned embodiments, R³³ isC₂₋₂₀ heterocyclyl or C₂₋₂₀ heteroaryl, each of which is optionallysubstituted one or more times by substituents selected independentlyfrom R⁴¹, wherein any two adjacent R⁴¹ optionally combine to form aring, which is optionally substituted one or more times withsubstituents selected independently from R^(x); or R³³ is C₂₋₂₀heteroalkyl, which is optionally substituted one or more times bysubstituents selected independently from R⁴².

In some embodiments of any of the aforementioned embodiments, R¹¹, R¹⁵,R¹⁶, R¹⁷ and R¹⁸ are independently a hydrogen atom, a halogen atom,C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀ heteroaryl, —CN,—O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹, —C(O)—R²¹, —O—C(O)—R²¹,—O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²², —C(O)—NR²¹R²², —N(R²¹)—C(O)—R²²,—N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²², —N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²²,—N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or —O—SiR²¹R²²R²³, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R³¹, wherein any two adjacent R³¹ optionally combine to form aring, which is optionally substituted one or more times withsubstituents selected independently from R^(x).

In some embodiments of any of the aforementioned embodiments, R³¹ is ahalogen atom, C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₁₂cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀ heteroaryl, —CN,—O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹, —C(O)—R²¹, —O—C(O)—R²¹,—O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²², —C(O)—NR²¹R²², —N(R²¹)—C(O)—R²²,—N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²², —N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²²,—N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or —O—SiR²¹R²²R²³, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R⁴¹, wherein any two adjacent R⁴¹ optionally combine to form aring, which is optionally substituted one or more times withsubstituents selected independently from R^(x), and wherein the alkyl,alkenyl, and alkynyl groups are optionally substituted one or more timeswith substituents selected independently from R⁴².

In some embodiments of any of the aforementioned embodiments, R³² is ahalogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀heteroaryl, —CN, —O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹,—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²²,—C(O)—NR²¹R²², —N(R²¹)—C(O)—R²², —N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²²,—N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²², —N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or—O—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R⁴¹, wherein any two adjacentR⁴¹ optionally combine to form a ring, which is optionally substitutedone or more times with substituents selected independently from R^(x).

In some embodiments of any of the aforementioned embodiments, R⁴¹ is ahalogen atom, C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₁₂cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀ heteroaryl, —CN,—O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹, —C(O)—R²¹, —O—C(O)—R²¹,—O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²², —C(O)—NR²¹R²², —N(R²¹)—C(O)—R²²,—N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²², —N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²²,—N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or —O—SiR²¹R²²R²³, wherein thecycloalkyl, heterocyclyl, aryl, and heteroaryl groups are optionallysubstituted one or more times with substituents selected independentlyfrom R^(x), and wherein the alkyl, alkenyl, and alkynyl groups areoptionally substituted one or more times with substituents selectedindependently from R^(y).

In some embodiments of any of the aforementioned embodiments, R⁴² is ahalogen atom, C₃₋₁₂ cycloalkyl, C₂₋₁₂ heterocyclyl, C₆₋₂₀ aryl, C₂₋₂₀heteroaryl, —CN, —O—R²¹, —S(O)_(w)—R²¹, —SO₂—O—R²¹, —O—SO₂—R²¹,—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—R²¹, —O—C(O)—O—R²¹, —NR²¹R²²,—C(O)—NR²¹R²², —N(R²¹)—C(O)—R²², —N(R²¹)—C(O)—O—R²², —O—C(O)—NR²¹R²²,—N(R²¹)—C(O)—NR²²R²³, —SO₂—NR²¹R²², —N(R²¹)—SO₂—R²², —SiR²¹R²²R²³, or—O—SiR²¹R²²R²³, wherein the cycloalkyl, heterocyclyl, aryl, andheteroaryl groups are optionally substituted one or more times withsubstituents selected independently from R^(x).

In some embodiments of any of the aforementioned embodiments, R^(x) is ahalogen atom, C₁₋₆ alkyl, C₃₋₁₀cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆alkyl), —SO₂(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂,—C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆ alkyl)₃, or—O—Si(C₁₋₆ alkyl)₃.

In some embodiments of any of the aforementioned embodiments, R^(y) is ahalogen atom, C₃₋₁₀cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆ alkyl),—SO₂(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —C(O)NH₂,—C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆ alkyl)₃, or—O—Si(C₁₋₆ alkyl)₃.

In some embodiments of any of the aforementioned embodiments, M is achromium atom, a molybdenum atom, or a tungsten atom. In some suchembodiments of any of the aforementioned embodiments, M is a molybdenumatom or a tungsten atom. In some embodiments of any of theaforementioned embodiments, M is a molybdenum atom. In some embodimentsof any of the aforementioned embodiments, M is a tungsten atom.

In some further embodiments of any of the aforementioned embodiments, nis 1. In some other embodiments of any of the aforementionedembodiments, n is 0.

In some further embodiments of any of the aforementioned embodiments, Xis an oxygen atom. In some other embodiments of any of theaforementioned embodiments, X is ═N—R⁵. In some other embodiments of anyof the aforementioned embodiments, X is ═N—N(R⁵)(R^(5′)). In some otherembodiments of any of the aforementioned embodiments, X is ═N—O—R⁵. Insome embodiments of any of the aforementioned embodiments, R⁵ and R^(5′)are independently C₃₋₁₂ cycloalkyl, C₆₋₂₀ aryl, or C₂₋₂₀ heteroaryl,each of which is optionally substituted one or more times withsubstituents selected independently from R³¹, wherein any two adjacentR³¹ optionally combine to form a ring, which is optionally substitutedone or more times with substituents selected independently from R^(x).In some further embodiments of any of the aforementioned embodiments, R⁵and R^(5′) are independently C₃₋₁₂ cycloalkyl, phenyl, 2-pyridinyl,3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl,4-pyrimidinyl, 5-pyrimidinyl, or 2-pyrazinyl, each of which isoptionally substituted one or more times with substituents selectedindependently from R³¹ wherein any two adjacent R³¹ optionally combineto form a ring, which is optionally substituted one or more times withsubstituents selected independently from R^(x). In some furtherembodiments of any of the aforementioned embodiments, R⁵ and R^(5′) areindependently C₃₋₁₂ cycloalkyl, phenyl, 2-pyridinyl, 3-pyridinyl,4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl,5-pyrimidinyl, or 2-pyrazinyl, each of which is optionally substitutedone or more times by substituents selected independently from the groupconsisting of a halogen atom, C₁₋₆ alkyl, C₃₋₁₀ cycloalkyl, phenyl, —CN,—OH, —O(C₁₋₆ alkyl), —SO₂(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆alkyl)₂, —C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆alkyl)₃, and —O—Si(C₁₋₆ alkyl)₃. In some further embodiments of any ofthe aforementioned embodiments, R⁵ and R^(5′) are independently C₃₋₁₂cycloalkyl or phenyl, each of which is optionally substituted one ormore times by substituents selected independently from the groupconsisting of a halogen atom, C₁₋₆ alkyl, C₃₋₁₀ cycloalkyl, phenyl, —CN,—OH, —O(C₁₋₆ alkyl), —SO₂(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆alkyl)₂, —C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆alkyl)₃, and —O—Si(C₁₋₆ alkyl)₃. In some further embodiments of any ofthe aforementioned embodiments, R⁵ and R^(5′) are independently C₃₋₁₂cycloalkyl or phenyl, each of which is optionally substituted one ormore times by substituents selected independently from the groupconsisting of a halogen atom and C₁₋₆ alkyl. In some further embodimentsof any of the aforementioned embodiments, R⁵ and R^(5′) areindependently adamantyl or phenyl, each of which is optionallysubstituted one or more times by substituents selected independentlyfrom the group consisting of a halogen atom and C₁₋₆ alkyl. In somefurther embodiments of any of the aforementioned embodiments, R⁵ andR^(5′) are independently 1-adamantyl, which is optionally substitutedone or more times by substituents selected independently from the groupconsisting of a halogen atom and C₁₋₆ alkyl. In some further embodimentsof any of the aforementioned embodiments, R⁵ and R^(5′) areindependently phenyl, which is optionally substituted one or more timesby substituents selected independently from the group consisting of ahalogen atom and C₁₋₆ alkyl. In some embodiments of any of theaforementioned embodiments, the phenyl group is substituted at the 2 and6 positions, for example, with substituents selected independently fromthe group consisting of a halogen atom and a C₁₋₆ alkyl group. In somefurther embodiments of any of the aforementioned embodiments, the phenylgroup is substituted at the 2 and 6 positions, for example, withsubstituents selected independently from the group consisting of achlorine atom, a methyl group, an ethyl group, and an isopropyl group.In some further embodiments of any of the aforementioned embodiments,the substituents at the 2 and 6 positions on the phenyl are the same; inother embodiments of any of the aforementioned embodiments, they aredifferent. In some further embodiments of any of the aforementionedembodiments, R⁵ and R^(5′) are independently selected independently fromthe group consisting of phenyl, 2,6-dimethylphenyl, 2,6-dichlorophenyl,and 2,6-diisopropylphenyl. In some further embodiments of any of theaforementioned embodiments, R⁵ and R^(5′) are independently selectedindependently from the group consisting of 2,6-dimethylphenyl,2,6-dichlorophenyl, and 2,6-diisopropylphenyl.

In some further embodiments of any of the aforementioned embodiments, R¹is hydrogen, C₁₋₆ alkyl, or —O—(C₁₋₆ alkyl). In some embodiments of anyof the aforementioned embodiments, R¹ is a hydrogen atom. In some otherembodiments of any of the aforementioned embodiments, R¹ is C₁₋₆ alkyl,such as methyl, ethyl, or isopropyl. In some other embodiments of any ofthe aforementioned embodiments, R¹ is —O—(C₁₋₆ alkyl), such as methoxy,ethoxy, or isopropoxy.

In some further embodiments of any of the aforementioned embodiments, R²is phenyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl,4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, or2-pyrazinyl, each of which is optionally substituted one or more timesby substituents selected independently from R⁶, wherein any two adjacentR⁶ optionally combine to form a ring, which is optionally substitutedone or more times by substituents selected independently from R^(x). Insome further embodiments of any of the aforementioned embodiments, R² isphenyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl,4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, or2-pyrazinyl, each of which is optionally substituted one or more timesby substituents selected independently from the group consisting of ahalogen atom, C₁₋₆ alkyl, C₃₋₁₀ cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆alkyl), —SH, —S(C₁₋₆ alkyl), —C(O)—(C₁₋₆ alkyl), —CHO, —O—C(O)—(C₁₋₆alkyl), —C(O)—O—(C₁₋₆ alkyl), —CO₂H, —O—C(O)—O—(C₁₋₆ alkyl), —SO₂(C₁₋₆alkyl), —O—SO₂(C₁₋₆ alkyl), —SO₂—O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl),—N(C₁₋₆ alkyl)₂, —C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂,—NH—CO₂H, —N(C₁₋₆ alkyl)-CO₂H, —NH—C(O)—O(C₁₋₆ alkyl), —N(C₁₋₆alkyl)-C(O)—O—(C₁₋₆ alkyl), —O—C(O)NH₂, —O—C(O)NH(C₁₋₆ alkyl),—O—C(O)N(C₁₋₆ alkyl)₂, —NH—C(O)NH₂, —NH—C(O)NH(C₁₋₆ alkyl),—NH—C(O)N(C₁₋₆ alkyl)₂, —N(C₁₋₆ alkyl)-C(O)NH₂, —N(C₁₋₆alkyl)-C(O)NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆alkyl)₃, —O—Si(C₁₋₆ alkyl)₃, —(C₁₋₆ alkylene)-C₃₋₁₀ cycloalkyl, —(C₁₋₆alkylene)-phenyl, —(C₁₋₆ alkylene)-CN, —(C₁₋₆ alkylene)-OH, —(C₁₋₆alkylene)-O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SH, —(C₁₋₆ alkylene)-S(C₁₋₆alkyl), —(C₁₋₆ alkylene)-C(O)—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-CHO, —(C₁₋₆alkylene)-O—C(O)—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)—O—(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-CO₂H, —(C₁₋₆ alkylene)-O—C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-SO₂(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—SO₂(C₁₋₆ alkyl), —(C₁₋₆alkylene)-SO₂—O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-NH₂, —(C₁₋₆alkylene)-NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)₂, —(C₁₋₆alkylene)-C(O)NH₂, —(C₁₋₆ alkylene)-C(O)NH(C₁₋₆ alkyl), —(C₁₋₆alkylene)-C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-NH—CO₂H, —(C₁₋₆alkylene)-N(C₁₋₆ alkyl)-CO₂H, —(C₁₋₆ alkylene)-NH—C(O)—O(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-O—C(O)NH₂, —(C₁₋₆ alkylene)-O—C(O)NH(C₁₋₆ alkyl), —(C₁₋₆alkylene)-O—C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-NH—C(O)NH₂, —(C₁₋₆alkylene)-NH—C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-NH—C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)NH₂, —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)N(C₁₋₆alkyl)₂, —(C₁₋₆ alkylene)-Si(C₁₋₆ alkyl)₃, and —(C₁₋₆alkylene)-O—Si(C₁₋₆ alkyl)₃. In some embodiments of any of theaforementioned embodiments, R² is phenyl, which is optionallysubstituted one or more times by substituents selected independentlyfrom R⁶, wherein any two adjacent R⁶ optionally combine to form a ring.In some embodiments of any of the aforementioned embodiments, R² isphenyl, which is optionally substituted one or more times bysubstituents selected independently from the group consisting of ahalogen atom, C₁₋₆ alkyl, C₃₋₁₀ cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆alkyl), —SH, —S(C₁₋₆ alkyl), —C(O)—(C₁₋₆ alkyl), —CHO, —O—C(O)—(C₁₋₆alkyl), —C(O)—O—(C₁₋₆ alkyl), —CO₂H, —O—C(O)—O—(C₁₋₆ alkyl), —SO₂(C₁₋₆alkyl), —O—SO₂(C₁₋₆ alkyl), —SO₂—O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl),—N(C₁₋₆ alkyl)₂, —C(O)NH₂, —C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂,—NH—CO₂H, —N(C₁₋₆ alkyl)-CO₂H, —NH—C(O)—O(C₁₋₆ alkyl), —N(C₁₋₆alkyl)-C(O)—O—(C₁₋₆ alkyl), —O—C(O)NH₂, —O—C(O)NH(C₁₋₆ alkyl),—O—C(O)N(C₁₋₆ alkyl)₂, —NH—C(O)NH₂, —NH—C(O)NH(C₁₋₆ alkyl),—NH—C(O)N(C₁₋₆ alkyl)₂, —N(C₁₋₆ alkyl)-C(O)NH₂, —N(C₁₋₆alkyl)-C(O)NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂, —Si(C₁₋₆alkyl)₃, —O—Si(C₁₋₆ alkyl)₃, —(C₁₋₆ alkylene)-C₃₋₁₀ cycloalkyl, —(C₁₋₆alkylene)-phenyl, —(C₁₋₆ alkylene)-CN, —(C₁₋₆ alkylene)-OH, —(C₁₋₆alkylene)-O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SH, —(C₁₋₆ alkylene)-S(C₁₋₆alkyl), —(C₁₋₆ alkylene)-C(O)—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-CHO, —(C₁₋₆alkylene)-O—C(O)—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)—O—(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-CO₂H, —(C₁₋₆ alkylene)-O—C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-SO₂(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—SO₂(C₁₋₆ alkyl), —(C₁₋₆alkylene)-SO₂—O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-NH₂, —(C₁₋₆alkylene)-NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)₂, —(C₁₋₆alkylene)-C(O)NH₂, —(C₁₋₆ alkylene)-C(O)NH(C₁₋₆ alkyl), —(C₁₋₆alkylene)-C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-NH—CO₂H, —(C₁₋₆alkylene)-N(C₁₋₆ alkyl)-CO₂H, —(C₁₋₆ alkylene)-NH—C(O)—O(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-O—C(O)NH₂, —(C₁₋₆ alkylene)-O—C(O)NH(C₁₋₆ alkyl), —(C₁₋₆alkylene)-O—C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-NH—C(O)NH₂, —(C₁₋₆alkylene)-NH—C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-NH—C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)NH₂, —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)N(C₁₋₆alkyl)₂, —(C₁₋₆ alkylene)-Si(C₁₋₆ alkyl)₃, and —(C₁₋₆alkylene)-O—Si(C₁₋₆ alkyl)₃. In some further embodiments of any of theaforementioned embodiments, R² is phenyl, which is optionallysubstituted one or more times with substituents selected independentlyfrom a halogen atom, —OH, —O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-OH, —(C₁₋₆alkylene)-O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —(C₁₋₆alkylene)-NH₂, —(C₁₋₆ alkylene)-NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)₂, and —NO₂. In some further embodiments of any of theaforementioned embodiments, R² is phenyl, which is optionallysubstituted one or more times with substituents selected independentlyfrom a halogen atom, —OH, —O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-OH, —(C₁₋₆alkylene)-O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —(C₁₋₆alkylene)-NH₂, —(C₁₋₆ alkylene)-NH(C₁₋₆ alkyl), and —(C₁₋₆alkylene)-N(C₁₋₆ alkyl)₂. In some further embodiments of any of theaforementioned embodiments, R² is unsubstituted phenyl. In some furtherembodiments of any of the aforementioned embodiments, R² is phenyl,which is optionally substituted one or more times by substituentsselected independently from a fluorine atom, methyl, methoxy, ethoxy,isopropxy, methoxymethyl, —N(CH₃)₂, and —NO₂.

In some embodiments of any of the aforementioned embodiments, R² is2-pyridyl, which is optionally substituted one or more times bysubstituents selected independently from R⁶, wherein any two adjacent R⁶optionally combine to form a ring. In some embodiments of any of theaforementioned embodiments, R² is 2-pyridyl, which is optionallysubstituted one or more times by substituents selected independentlyfrom the group consisting of a halogen atom, C₁₋₆ alkyl, C₃₋₁₀cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆ alkyl), —SH, —S(C₁₋₆ alkyl),—C(O)—(C₁₋₆ alkyl), —CHO, —O—C(O)—(C₁₋₆ alkyl), —C(O)—O—(C₁₋₆ alkyl),—CO₂H, —O—C(O)—O—(C₁₋₆ alkyl), —SO₂(C₁₋₆ alkyl), —O—SO₂(C₁₋₆ alkyl),—SO₂—O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —C(O)NH₂,—C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —NH—CO₂H, —N(C₁₋₆ alkyl)-CO₂H,—NH—C(O)—O(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)—O—(C₁₋₆ alkyl), —O—C(O)NH₂,—O—C(O)NH(C₁₋₆ alkyl), —O—C(O)N(C₁₋₆ alkyl)₂, —NH—C(O)NH₂,—NH—C(O)NH(C₁₋₆ alkyl), —NH—C(O)N(C₁₋₆ alkyl)₂, —N(C₁₋₆ alkyl)-C(O)NH₂,—N(C₁₋₆ alkyl)-C(O)NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂,—Si(C₁₋₆ alkyl)₃, —O—Si(C₁₋₆ alkyl)₃, —(C₁₋₆ alkylene)-C₃₋₁₀ cycloalkyl,—(C₁₋₆ alkylene)-phenyl, —(C₁₋₆ alkylene)-CN, —(C₁₋₆ alkylene)-OH,—(C₁₋₆ alkylene)-O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SH, —(C₁₋₆alkylene)-S(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-CHO, —(C₁₋₆ alkylene)-O—C(O)—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-CO₂H, —(C₁₋₆alkylene)-O—C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SO₂(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-O—SO₂(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SO₂—O(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-NH₂, —(C₁₋₆ alkylene)-NH(C₁₋₆ alkyl), —(C₁₋₆alkylene)-N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-C(O)NH₂, —(C₁₋₆alkylene)-C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-NH—CO₂H, —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-CO₂H, —(C₁₋₆alkylene)-NH—C(O)—O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—C(O)NH₂, —(C₁₋₆alkylene)-O—C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-NH—C(O)NH₂, —(C₁₋₆ alkylene)-NH—C(O)NH(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-NH—C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)NH₂, —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)NH(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆alkylene)-Si(C₁₋₆ alkyl)₃, and —(C₁₋₆ alkylene)-O—Si(C₁₋₆ alkyl)₃. Insome further embodiments of any of the aforementioned embodiments, R² is2-pyridyl, which is optionally substituted one or more times withsubstituents selected independently from a halogen atom, —OH, —O(C₁₋₆alkyl), —(C₁₋₆ alkylene)-OH, —(C₁₋₆ alkylene)-O(C₁₋₆ alkyl), —NH₂,—NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-NH₂, —(C₁₋₆alkylene)-NH(C₁₋₆ alkyl), and —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)₂. In someembodiments of any of the aforementioned embodiments, R² isunsubstituted 2-pyridyl.

In some further embodiments of any of the aforementioned embodiments, R²is 2-(C₁₋₆ alkyloxy)phenyl, where the phenyl ring is further optionallysubstituted one or more times by substituents selected independentlyfrom the group consisting of a halogen atom, C₁₋₆ alkyl, C₃₋₁₀cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆ alkyl), —SH, —S(C₁₋₆ alkyl),—C(O)—(C₁₋₆ alkyl), —CHO, —O—C(O)—(C₁₋₆ alkyl), —C(O)—O—(C₁₋₆ alkyl),—CO₂H, —O—C(O)—O—(C₁₋₆ alkyl), —SO₂(C₁₋₆ alkyl), —O—SO₂(C₁₋₆ alkyl),—SO₂—O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —C(O)NH₂,—C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —NH—CO₂H, —N(C₁₋₆ alkyl)-CO₂H,—NH—C(O)—O(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)—O—(C₁₋₆ alkyl), —O—C(O)NH₂,—O—C(O)NH(C₁₋₆ alkyl), —O—C(O)N(C₁₋₆ alkyl)₂, —NH—C(O)NH₂,—NH—C(O)NH(C₁₋₆ alkyl), —NH—C(O)N(C₁₋₆ alkyl)₂, —N(C₁₋₆ alkyl)-C(O)NH₂,—N(C₁₋₆ alkyl)-C(O)NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂,—Si(C₁₋₆ alkyl)₃, —O—Si(C₁₋₆ alkyl)₃, —(C₁₋₆ alkylene)-C₃₋₁₀ cycloalkyl,—(C₁₋₆ alkylene)-phenyl, —(C₁₋₆ alkylene)-CN, —(C₁₋₆ alkylene)-OH,—(C₁₋₆ alkylene)-O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SH, —(C₁₋₆alkylene)-S(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-CHO, —(C₁₋₆ alkylene)-O—C(O)—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-CO₂H, —(C₁₋₆alkylene)-O—C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SO₂(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-O—SO₂(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SO₂—O(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-NH₂, —(C₁₋₆ alkylene)-NH(C₁₋₆ alkyl), —(C₁₋₆alkylene)-N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-C(O)NH₂, —(C₁₋₆alkylene)-C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-NH—CO₂H, —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-CO₂H, —(C₁₋₆alkylene)-NH—C(O)—O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—C(O)NH₂, —(C₁₋₆alkylene)-O—C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-NH—C(O)NH₂, —(C₁₋₆ alkylene)-NH—C(O)NH(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-NH—C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)NH₂, —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)NH(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆alkylene)-Si(C₁₋₆ alkyl)₃, and —(C₁₋₆ alkylene)-O—Si(C₁₋₆ alkyl)₃. Insome embodiments of any of the aforementioned embodiments, R² is 2-(C₁₋₆alkyloxy)phenyl, which is optionally substituted one or more times withsubstituents selected independently from a halogen atom, —OH, —O(C₁₋₆alkyl), —(C₁₋₆ alkylene)-OH, —(C₁₋₆ alkylene)-O(C₁₋₆ alkyl), —NH₂,—NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-NH₂, —(C₁₋₆alkylene)-NH(C₁₋₆ alkyl), and —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)₂. In somefurther such embodiments of any of the aforementioned embodiments, R² is2-methoxyphenyl, 2-ethoxyphenyl, or 2-isopropoxyphenyl, each of which isoptionally substituted as indicated in any of the above embodiments ofthis paragraph. In some even further embodiments, R² is 2-methoxyphenyl,which is optionally substituted as indicated in any of the aboveembodiments. In some further embodiments of any of the aforementionedembodiments, R² is 2-methoxyphenyl, 2-ethoxyohenyl, or2-isopropxyphenyl, each of which is optionally substituted one or moretimes by substituents selected independently from the group consistingof methyl, methoxy, and a fluorine atom. In some embodiments of any ofthe aforementioned embodiments, R² is 2-methoxyphenyl, 2-ethoxyphenyl,2-isopropxyphenyl, 2-methoxy-4-fluorophenyl, 2-methoxy-5-fluorophenyl,2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,4,5-trimethoxyphenyl, or2-methoxy-4-methylphenyl.

In some further embodiments of any of the aforementioned embodiments, R²is 2-(C₁₋₆ alkyloxymethyl)phenyl, where the phenyl ring is furtheroptionally substituted one or more times by substituents selectedindependently from the group consisting of a halogen atom, C₁₋₆ alkyl,C₃₋₁₀ cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆ alkyl), —SH, —S(C₁₋₆ alkyl),—C(O)—(C₁₋₆ alkyl), —CHO, —O—C(O)—(C₁₋₆ alkyl), —C(O)—O—(C₁₋₆ alkyl),—CO₂H, —O—C(O)—O—(C₁₋₆ alkyl), —SO₂(C₁₋₆ alkyl), —O—SO₂(C₁₋₆ alkyl),—SO₂—O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —C(O)NH₂,—C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —NH—CO₂H, —N(C₁₋₆ alkyl)-CO₂H,—NH—C(O)—O(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)—O—(C₁₋₆ alkyl), —O—C(O)NH₂,—O—C(O)NH(C₁₋₆ alkyl), —O—C(O)N(C₁₋₆ alkyl)₂, —NH—C(O)NH₂,—NH—C(O)NH(C₁₋₆ alkyl), —NH—C(O)N(C₁₋₆ alkyl)₂, —N(C₁₋₆ alkyl)-C(O)NH₂,—N(C₁₋₆ alkyl)-C(O)NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂,—Si(C₁₋₆ alkyl)₃, —O—Si(C₁₋₆ alkyl)₃, —(C₁₋₆ alkylene)-C₃₋₁₀ cycloalkyl,—(C₁₋₆ alkylene)-phenyl, —(C₁₋₆ alkylene)-CN, —(C₁₋₆ alkylene)-OH,—(C₁₋₆ alkylene)-O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SH, —(C₁₋₆alkylene)-S(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-CHO, —(C₁₋₆ alkylene)-O—C(O)—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-CO₂H, —(C₁₋₆alkylene)-O—C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SO₂(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-O—SO₂(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SO₂—O(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-NH₂, —(C₁₋₆ alkylene)-NH(C₁₋₆ alkyl), —(C₁₋₆alkylene)-N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-C(O)NH₂, —(C₁₋₆alkylene)-C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-NH—CO₂H, —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-CO₂H, —(C₁₋₆alkylene)-NH—C(O)—O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—C(O)NH₂, —(C₁₋₆alkylene)-O—C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-NH—C(O)NH₂, —(C₁₋₆ alkylene)-NH—C(O)NH(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-NH—C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)NH₂, —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)NH(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆alkylene)-Si(C₁₋₆ alkyl)₃, and —(C₁₋₆ alkylene)-O—Si(C₁₋₆ alkyl)₃. Insome embodiments of any of the aforementioned embodiments, R² is 2-(C₁₋₆alkyloxymethyl)phenyl, which is optionally substituted one or more timeswith substituents selected independently from a halogen atom, —OH,—O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-OH, —(C₁₋₆ alkylene)-O(C₁₋₆ alkyl),—NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-NH₂, —(C₁₋₆alkylene)-NH(C₁₋₆ alkyl), and —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)₂. In somefurther embodiments of any of the aforementioned embodiments, R² is2-(methoxymethyl)phenyl, 2-(ethoxymethyl)phenyl, or2-(isopropoxymethyl)phenyl, each of which is optionally substituted asindicated in any of the above embodiments of this paragraph. In someeven further embodiments of any of the aforementioned embodiments, R² is2-(methoxymethyl)phenyl, which is optionally substituted as indicated inany of the above embodiments of this paragraph. In some furtherembodiments of any of the aforementioned embodiments, R² is2-(methoxymethyl)phenyl.

In some further embodiments of any of the aforementioned embodiments, R²is 2-[—N(C₁₋₆ alkyl)₂]phenyl, where the phenyl ring is furtheroptionally substituted one or more times by substituents selectedindependently from the group consisting of a halogen atom, C₁₋₆ alkyl,C₃₋₁₀ cycloalkyl, phenyl, —CN, —OH, —O(C₁₋₆ alkyl), —SH, —S(C₁₋₆ alkyl),—C(O)—(C₁₋₆ alkyl), —CHO, —O—C(O)—(C₁₋₆ alkyl), —C(O)—O—(C₁₋₆ alkyl),—CO₂H, —O—C(O)—O—(C₁₋₆ alkyl), —SO₂(C₁₋₆ alkyl), —O—SO₂(C₁₋₆ alkyl),—SO₂—O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —C(O)NH₂,—C(O)NH(C₁₋₆ alkyl), —C(O)N(C₁₋₆ alkyl)₂, —NH—CO₂H, —N(C₁₋₆ alkyl)-CO₂H,—NH—C(O)—O(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)—O—(C₁₋₆ alkyl), —O—C(O)NH₂,—O—C(O)NH(C₁₋₆ alkyl), —O—C(O)N(C₁₋₆ alkyl)₂, —NH—C(O)NH₂,—NH—C(O)NH(C₁₋₆ alkyl), —NH—C(O)N(C₁₋₆ alkyl)₂, —N(C₁₋₆ alkyl)-C(O)NH₂,—N(C₁₋₆ alkyl)-C(O)NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂,—Si(C₁₋₆ alkyl)₃, —O—Si(C₁₋₆ alkyl)₃, —(C₁₋₆ alkylene)-C₃₋₁₀ cycloalkyl,—(C₁₋₆ alkylene)-phenyl, —(C₁₋₆ alkylene)-CN, —(C₁₋₆ alkylene)-OH,—(C₁₋₆ alkylene)-O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SH, —(C₁₋₆alkylene)-S(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-CHO, —(C₁₋₆ alkylene)-O—C(O)—(C₁₋₆ alkyl), —(C₁₋₆alkylene)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-CO₂H, —(C₁₋₆alkylene)-O—C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SO₂(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-O—SO₂(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-SO₂—O(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-NH₂, —(C₁₋₆ alkylene)-NH(C₁₋₆ alkyl), —(C₁₋₆alkylene)-N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-C(O)NH₂, —(C₁₋₆alkylene)-C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-NH—CO₂H, —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-CO₂H, —(C₁₋₆alkylene)-NH—C(O)—O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)—O—(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—C(O)NH₂, —(C₁₋₆alkylene)-O—C(O)NH(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-O—C(O)N(C₁₋₆ alkyl)₂,—(C₁₋₆ alkylene)-NH—C(O)NH₂, —(C₁₋₆ alkylene)-NH—C(O)NH(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-NH—C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-N(C₁₋₆alkyl)-C(O)NH₂, —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)NH(C₁₋₆ alkyl),—(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)-C(O)N(C₁₋₆ alkyl)₂, —(C₁₋₆alkylene)-Si(C₁₋₆ alkyl)₃, and —(C₁₋₆ alkylene)-O—Si(C₁₋₆ alkyl)₃. Insome embodiments of any of the aforementioned embodiments, R² is 2-(C₁₋₆alkyloxymethyl)phenyl, which is optionally substituted one or more timeswith substituents selected independently from a halogen atom, —OH,—O(C₁₋₆ alkyl), —(C₁₋₆ alkylene)-OH, —(C₁₋₆ alkylene)-O(C₁₋₆ alkyl),—NH₂, —NH(C₁₋₆ alkyl), —N(C₁₋₆ alkyl)₂, —(C₁₋₆ alkylene)-NH₂, —(C₁₋₆alkylene)-NH(C₁₋₆ alkyl), and —(C₁₋₆ alkylene)-N(C₁₋₆ alkyl)₂. In somefurther embodiments of any of the aforementioned embodiments, R² is2-(dimethylamino)phenyl, which is optionally substituted as indicated inany of the above embodiments of this paragraph. In some even furtherembodiments of any of the aforementioned embodiments, R² is2-(dimethylamino)phenyl.

In some embodiments of any of the aforementioned embodiments, R² is-G¹⁰-R³³. In some embodiments of any of the aforementioned embodiments,G¹⁰ is —O—. In some other embodiments of any of the aforementionedembodiments, G¹⁰ is —S—.

In some other embodiments of any of the aforementioned embodiments, G¹⁰is —Se—. In some other embodiments of any of the aforementionedembodiments, G¹⁰ is —C(R²¹)(R²²)—. In some other embodiments of any ofthe aforementioned embodiments, G¹⁰ is —Si(R²¹)(R²²). In some otherembodiments of any of the aforementioned embodiments, G¹⁰ is —N(R²¹)—.

In some further such embodiments of any of the aforementionedembodiments, R³³ is C₂₋₂₀ heterocyclyl, which is optionally substitutedone or more times by substituents selected independently from R⁴¹,wherein any two adjacent R⁴¹ optionally combine to form a ring, which isoptionally substituted one or more times with substituents selectedindependently from R^(x). In some embodiments of any of theaforementioned embodiments, the heterocyclyl group has a heteroatom atthe 2-position relative to the attachment point of the heterocyclylgroup to G¹⁰, wherein said heteroatom is an oxygen atom, a sulfur atom,a selenium atom, or a nitrogen atom. In some embodiments of any of theaforementioned embodiments, said heteroatom is an oxygen atom. In someother embodiments of any of the aforementioned embodiments, saidheteroatom is a sulfur atom. In some other embodiments of any of theaforementioned embodiments, said heteroatom is a nitrogen atom.

In some embodiments of any of the aforementioned embodiments, R³³ is2-tetrahydropyranyl, which is optionally substituted one or more timesby substituents selected independently from R⁴¹, wherein any twoadjacent R⁴¹ optionally combine to form a ring, which is optionallysubstituted one or more times with substituents selected independentlyfrom R^(x). In some embodiments of any of the aforementionedembodiments, R³³ is unsubstituted 2-tetrahydropyranyl.

In some further such embodiments of any of the aforementionedembodiments, R³³ is C₂₋₂₀ heteroaryl, which is optionally substitutedone or more times by substituents selected independently from R⁴¹,wherein any two adjacent R⁴¹ optionally combine to form a ring, which isoptionally substituted one or more times with substituents selectedindependently from R^(x). In some embodiments of any of theaforementioned embodiments, the heteroaryl group has a heteroatom at the2-position relative to the attachment point of the heteroaryl group toG¹⁰, wherein said heteroatom is an oxygen atom, a sulfur atom, aselenium atom, or a nitrogen atom. In some embodiments of any of theaforementioned embodiments, said heteroatom is a nitrogen atom.

In some embodiments of any of the aforementioned embodiments, R³³ is2-pyridyl, which is optionally substituted one or more times bysubstituents selected independently from R⁴¹, wherein any two adjacentR⁴¹ optionally combine to form a ring, which is optionally substitutedone or more times with substituents selected independently from R^(x).In some embodiments of any of the aforementioned embodiments, R³³ isunsubstituted 2-pyridyl.

In some further such embodiments of any of the aforementionedembodiments, R³³ is C₂₋₂₀ heteroalkyl, which is optionally substitutedone or more times by substituents selected independently from R⁴². Insome embodiments of any of the aforementioned embodiments, theheteroalkyl group has a heteroatom at the 2-position relative to theattachment point of the heteroalkyl group to G¹⁰, wherein saidheteroatom is an oxygen atom, a sulfur atom, a selenium atom, or anitrogen atom. In some embodiments of any of the aforementionedembodiments, said heteroatom is an oxygen atom. In some other suchembodiments of any of the aforementioned embodiments, said heteroatom isa sulfur atom. In some other embodiments of any of the aforementionedembodiments, said heteroatom is a nitrogen atom.

In some embodiments of any of the aforementioned embodiments, R³³ is—CH₂—O—(C₁₋₁₀ alkyl), —CH(C₁₋₆ alkyl)-O—(C₁₋₁₀ alkyl), or —C(C₁₋₆alkyl)₂-O—(C₁₋₆ alkyl).

In some embodiments of any of the aforementioned embodiments, G¹⁰ is—NR²¹— and the R²¹ group combines with R³³ to form a nitrogen-containingheterocyclic ring, which is optionally substituted one or more timeswith substituents selected independently from R^(x), and wherein anycarbon atom of the ring is optionally oxidized to form a carbonyl group.In some such embodiments of any of the aforementioned embodiments, onecarbon atom immediately adjacent to the nitrogen atom is oxidized toform a carbonyl group. In some embodiments of any of the aforementionedembodiments, R² is pyrrolidin-2-on-1-yl, imidazolidin-2-on-1-yl,imidazolidin-5-on-1-yl, or piperidin-2-on-1-yl. In some embodiments ofany of the aforementioned embodiments, R² is pyrrolidin-2-on-1-yl.

In some embodiments of any of the aforementioned embodiments, R³³ is—C(O)—R⁴³. In some further embodiments of any of the aforementionedembodiments, R⁴³ is C₁₋₆ alkyl. In some further embodiments of any ofthe aforementioned embodiments, R⁴³ is methyl, ethyl, isopropyl, propyl,butyl, isobutyl, sec-butyl, or tert-butyl. In some further embodimentsof any of the aforementioned embodiments R⁴³ is methyl or tert-butyl. Insome further embodiments of any of the aforementioned embodiments, R⁴³is phenyl.

In some further embodiments of any of the aforementioned embodiments, R³is —OR⁷, —SR⁷, or —N(R⁷)(R^(7′)). In some further embodiments of any ofthe aforementioned embodiments, R³ is —OR⁷ or —SR⁷. In some embodimentsof any of the aforementioned embodiments, R³ is —SR⁷. In some otherembodiments of any of the aforementioned embodiments, R³ is —OR⁷. Insome other embodiments of any of the aforementioned embodiments, R³ is—N(R⁷)(R^(7′)). In some embodiments of any of the aforementionedembodiments, R⁷ is -G⁷-R¹⁷. In some further embodiments of any of theaforementioned embodiments, -G⁷-R¹⁷ is C₁₋₁₂ alkyl, which is optionallysubstituted one or more times with substituents selected independentlyfrom R³². In some even further embodiments of any of the aforementionedembodiments, -G⁷-R¹⁷ is C₁₋₁₂ alkyl, which is optionally substituted oneor more times with substituents selected independently from the groupconsisting of a halogen atom and phenyl, wherein the phenyl group isoptionally substituted one or more times with substituents selectedindependently from the group consisting of a halogen atom, C₁₋₆ alkyl,—O—(C₁₋₆ alkyl), C₁₋₆ haloalkyl, —O—(C₁₋₆ haloalkyl), —Si—(C₁₋₆ alkyl)₃,and —O—Si(C₁₋₆ alkyl)₃. In some even further embodiments of any of theaforementioned embodiments, -G⁷-R¹⁷ is C₁₋₁₂ alkyl, which is optionallysubstituted one or more times with substituents selected independentlyfrom the group consisting of a halogen atom and phenyl. In some furthersuch embodiments of any of the aforementioned embodiments, -G⁷-R¹⁷ istert-butyl, —C(CH₃)₂(CF₃), —C(CF₃)₃, or —C(CF₃)₂-(phenyl).

In some other embodiments of any of the aforementioned embodiments, R⁷is C₆₋₂₀ aryl or C₂₋₂₀ heteroaryl, each of which is optionallysubstituted one or more times with substituents selected independentlyfrom R³¹, wherein any two adjacent R³¹ optionally combine to form aring, which is optionally substituted one or more times withsubstituents selected independently from R^(x). In some further suchembodiments of any of the aforementioned embodiments, R⁷ is phenyl,1-naphthyl, or 2-naphthyl, each of which is optionally substituted oneor more times with substituents selected independently from the groupconsisting of a halogen atom, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₃₋₁₀cycloalkyl, phenyl, 1-naphthyl, 2-naphthyl, —CN, —O(C₁₋₆ alkyl),—Si(C₁₋₆ alkyl)₃, and —O—Si(C₁₋₆ alkyl)₃, or any two adjacentsubstituents can optionally combine to form a —(CH₂)₃— ring or a —(CH)₄—ring, wherein the cycloalkyl, phenyl, and naphthyl substituents areoptionally substituted one or more times by substituents selectedindependently from the group consisting of a halogen atom, C₁₋₆ alkyl,C₃₋₁₀cycloalkyl, phenyl, —CN, —O(C₁₋₆ alkyl), —Si(C₁₋₆ alkyl)₃, and—O—Si(C₁₋₆ alkyl)₃, or any two adjacent substituents can optionallycombine to form a —(CH₂)₃— ring or a —(CH)₄— ring. In some furtherembodiments of any of the aforementioned embodiments, R⁷ is phenyl or1-naphthyl, which is optionally substituted one or more times withsubstituents selected independently from the group consisting of ahalogen atom, C₁₋₆ alkyl, phenyl, 1-naphthyl, —O(C₁₋₆ alkyl), and—O—Si(C₁₋₆ alkyl)₃, or any two adjacent alkyl substituents canoptionally combine to form a —(CH₂)₄— ring, wherein the phenyl andnaphthyl substituents are optionally substituted one or more times bysubstituents selected independently from the group consisting of ahalogen atom, C₁₋₆ alkyl, phenyl, —O(C₁₋₆ alkyl), and —O—Si(C₁₋₆alkyl)₃, or any two adjacent alkyl substituents can optionally combineto form a —(CH₂)₄— ring.

In some further embodiments of any of the aforementioned embodiments, R⁷is phenyl, which is optionally substituted one or more times bysubstituents selected independently from the group consisting of ahalogen atom and phenyl. For example, in some such embodiments of any ofthe aforementioned embodiments, R⁷ is 2,6-diphenylphenyl or4-bromo-2,3,5,6-tetraphenylphenyl. In some further such embodiments ofany of the aforementioned embodiments, R⁷ is 2,3,5,6-tetraphenylphenyl.In some further embodiments of any of the aforementioned embodiments, R⁷is phenyl, which is optionally substituted one or more times bysubstituents selected independently from the group consisting of —NO₂(“nitro”) and phenyl. For example, in some such embodiments of any ofthe aforementioned embodiments, R⁷ is 4-nitro-2,3,5,6-tetraphenylphenyl.In some other embodiments of any of the aforementioned embodiments, R⁷is phenyl or naphthyl (e.g., 1-naphthyl), which are optionallysubstituted by one or more times by substituents selected independentlyfrom the group consisting of a halogen atom (e.g., fluoro, chloro, orbromo), C₁₋₆ alkyl (e.g., methyl, ethyl, isopropyl, tert-butyl, etc.),C₆₋₂₀ aryl (e.g., phenyl, naphthyl, etc.), —O—(C₁₋₆ alkyl) (e.g.,methoxy), and —O—Si(C₁₋₆ alkyl)₃ (e.g., tert-butyldimethylsilyloxy),with any two adjacent alkyl substituents optionally combining to form a—(CH₂)₄— ring, where the aryl groups are optionally further substitutedone or more times by substituents selected independently from the groupconsisting of a halogen atom (e.g., fluoro, chloro, or bromo), C₁₋₆alkyl (e.g., methyl, ethyl, isopropyl, tert-butyl, etc.), C₆₋₂₀ aryl(e.g., phenyl, naphthyl, etc.), —O—(C₁₋₆ alkyl) (e.g., methoxy), and—O—Si(C₁₋₆ alkyl)₃ (e.g., tert-butyldimethylsilyloxy). In someembodiments of any of the aforementioned embodiments, R⁷ is

wherein “iPr” refers to isopropyl, and “OTBDMS” refers totert-butyldimethylsilyloxy.

In some further embodiments of any of the aforementioned embodiments, R⁷is —SiR²¹R²²R²³. In some embodiments of any of the aforementionedembodiments, R⁷ is —Si—(C₁₋₆ alkyl)_(p)(phenyl)_(q), wherein p+q=3 and pand q can each be 0, 1, 2, or 3. In some embodiments of any of theaforementioned embodiments, R⁷ is —Si(phenyl)₃.

In some further embodiments of any of the aforementioned embodiments, R⁷is —CR²¹R²²R²³. In some embodiments of any of the aforementionedembodiments, R⁷ is —C—(C₁₋₆ alkyl)₃, wherein the alkyl groups areoptionally substituted one or more times with a halogen atom (e.g., afluorine atom). In some embodiments of any of the aforementionedembodiments, R⁷ is —C(CH₃)(CF₃)₂, —C(CH₃)₂(CF₃), —C(CF₃)₃. In somefurther embodiments of any of the aforementioned embodiments, R⁷ is—C(CH₃)(CF₃)₂.

In some other embodiments of any of the aforementioned embodiments,R^(7′) is a hydrogen atom. In some other embodiments of any of theaforementioned embodiments, R^(7′) is C₆₋₂₀ aryl or C₂₋₂₀ heteroaryl,each of which is optionally substituted one or more times withsubstituents selected independently from R³¹, wherein any two adjacentR³¹ optionally combine to form a ring, which is optionally substitutedone or more times with substituents selected independently from R^(x).In some further such embodiments of any of the aforementionedembodiments, R^(7′) is phenyl, 1-naphthyl, or 2-naphthyl, each of whichis optionally substituted one or more times with substituents selectedindependently from the group consisting of a halogen atom, C₁₋₆ alkyl,C₂₋₆ alkenyl, C₃₋₁₀ cycloalkyl, phenyl, 1-naphthyl, 2-naphthyl, —CN,—O(C₁₋₆ alkyl), —Si(C₁₋₆ alkyl)₃, and —O—Si(C₁₋₆ alkyl)₃, or any twoadjacent substituents can optionally combine to form a —(CH₂)₃— ring ora —(CH)₄— ring, wherein the cycloalkyl, phenyl, and naphthylsubstituents are optionally substituted one or more times bysubstituents selected independently from the group consisting of ahalogen atom, C₁₋₆ alkyl, C₃₋₁₀ cycloalkyl, phenyl, —CN, —O(C₁₋₆ alkyl),—Si(C₁₋₆ alkyl)₃, and —O—Si(C₁₋₆ alkyl)₃, or any two adjacentsubstituents can optionally combine to form a —(CH₂)₃— ring or a —(CH)₄—ring. In some further embodiments of any of the aforementionedembodiments, R^(7′) is phenyl or 1-naphthyl, which is optionallysubstituted one or more times with substituents selected independentlyfrom the group consisting of a halogen atom, C₁₋₆ alkyl, phenyl,1-naphthyl, —O(C₁₋₆ alkyl), and —O—Si(C₁₋₆ alkyl)₃, or any two adjacentalkyl substituents can optionally combine to form a —(CH₂)₄— ring,wherein the phenyl and naphthyl substituents are optionally substitutedone or more times by substituents selected independently from the groupconsisting of a halogen atom, C₁₋₆ alkyl, phenyl, —O(C₁₋₆ alkyl), and—O—Si(C₁₋₆ alkyl)₃, or any two adjacent alkyl substituents canoptionally combine to form a —(CH₂)₄— ring.

In some further embodiments of any of the aforementioned embodiments,R^(7′) is phenyl, which is optionally substituted one or more times bysubstituents selected independently from the group consisting of ahalogen atom and phenyl. For example, in some such embodiments of any ofthe aforementioned embodiments, R^(7′) is 2,6-diphenylphenyl or4-bromo-2,3,5,6-tetraphenylphenyl. In some further such embodiments ofany of the aforementioned embodiments, RT is 2,3,5,6-tetraphenylphenyl.In some further embodiments of any of the aforementioned embodiments,R^(7′) is phenyl, which is optionally substituted one or more times bysubstituents selected independently from the group consisting of —NO₂(“nitro”) and phenyl. For example, in some such embodiments of any ofthe aforementioned embodiments, R^(7′) is4-nitro-2,3,5,6-tetraphenylphenyl. In some other embodiments of any ofthe aforementioned embodiments, R⁷ is phenyl or naphthyl (e.g.,1-naphthyl), which are optionally substituted by one or more times bysubstituents selected independently from the group consisting of ahalogen atom (e.g., fluoro, chloro, or bromo), C₁₋₆ alkyl (e.g., methyl,ethyl, isopropyl, tert-butyl, etc.), C₆₋₂₀ aryl (e.g., phenyl, naphthyl,etc.), —O—(C₁₋₆ alkyl) (e.g., methoxy), and —O—Si(C₁₋₆ alkyl)₃ (e.g.,tert-butyldimethylsilyloxy), with any two adjacent alkyl substituentsoptionally combining to form a —(CH₂)₄— ring, where the aryl groups areoptionally further substituted one or more times by substituentsselected independently from the group consisting of a halogen atom(e.g., fluoro, chloro, or bromo), C₁₋₆ alkyl (e.g., methyl, ethyl,isopropyl, tert-butyl, etc.), C₆₋₂₀ aryl (e.g., phenyl, naphthyl, etc.),—O—(C₁₋₆ alkyl) (e.g., methoxy), and —O—Si(C₁₋₆ alkyl)₃ (e.g.,tert-butyldimethylsilyloxy). In some embodiments of any of theaforementioned embodiments, R^(7′) is:

wherein “iPr” refers to isopropyl, and “OTBDMS” refers totert-butyldimethylsilyloxy.

In some further embodiments of any of the aforementioned embodiments,R^(7′) is —SiR²¹R²²R²³. In some embodiments of any of the aforementionedembodiments, R⁷ is —Si—(C₁₋₆ alkyl)_(p)(phenyl)_(q), wherein p+q=3 and pand q can each be 0, 1, 2, or 3. In some embodiments of any of theaforementioned embodiments, RT is —Si(phenyl)₃.

In some further embodiments of any of the aforementioned embodiments,R^(7′) is —CR²¹R²²R²³. In some embodiments of any of the aforementionedembodiments, R^(7′) is —C—(C₁₋₆ alkyl)₃, wherein the alkyl groups areoptionally substituted one or more times with a halogen atom (e.g., afluorine atom). In some embodiments of any of the aforementionedembodiments, R^(7′) is —C(CH₃)(CF₃)₂, —C(CH₃)₂(CF₃), —C(CF₃)₃. In somefurther embodiments of any of the aforementioned embodiments, R^(7′) is—C(CH₃)(CF₃)₂.

In some further embodiments of any of the aforementioned embodiments, R⁴is —O—SiR²¹R²²R²³. In some embodiments of any of the aforementionedembodiments, R⁴ is —O—Si—(C₁₋₆ alkyl)_(r)(phenyl)_(s), wherein r+s=3 andr and s are each 0, 1, 2, or 3, and wherein the alkyl and phenyl groupsare each optionally substituted one or more times by a halogen atom(e.g., a fluorine atom). In some such embodiments of any of theaforementioned embodiments, R⁴ is —O—Si(phenyl)₃.

In some further embodiments of any of the aforementioned embodiments, R⁴is —O—CR²¹R²²R²³. In some such embodiments of any of the aforementionedembodiments, R⁴ is —O—C—(C₁₋₆ alkyl)_(v)(phenyl)_(w), wherein v+w=3 andv and w are each 0, 1, 2, or 3, and wherein the alkyl and phenyl groupsare each optionally substituted one or more times by a substituentsselected from a halogen atom (e.g., a fluorine atom) and —O—(C₁₋₆alkyl). In some such embodiments of any of the aforementionedembodiments, R⁴ is —O—C—(C₁₋₆ alkyl)_(v)(phenyl)_(w), wherein v+w=3 andv and w are each 0, 1, 2, or 3, and wherein the alkyl and phenyl groupsare each optionally substituted one or more times by a halogen atom(e.g., a fluorine atom). In some embodiments of any of theaforementioned embodiments, R⁴ is —O—C(CH₃)₂(CH₂—O—CH₃). In someembodiments of any of the aforementioned embodiments, R⁴ is—O—C(CF₃)₂(CH₃).

In some further embodiments of any of the aforementioned embodiments, R⁴is pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl, 1H-1,2,3-triazol-1-yl,2H-1,2,3-triazol-2-yl, 1H-1,2,4-triazol-1-yl, 4H-1,2,4-triazol-4-yl,indol-1-yl, indazol-1-yl, or azaindol-1-yl, each of which is optionallysubstituted one or more times with substituents selected independentlyfrom R⁸, wherein any two adjacent R⁸ optionally combine to form a ring,which is optionally substituted one or more times with substituentsselected independently from R^(x). In some further embodiments of any ofthe aforementioned embodiments, R⁴ is pyrrol-1-yl, pyrazol-1-yl,imidazol-1-yl, 1H-1,2,3-triazol-1-yl, 2H-1,2,3-triazol-2-yl,1H-1,2,4-triazol-1-yl, or 4H-1,2,4-triazol-4-yl, each of which isoptionally substituted one or more times with substituents selectedindependently from R⁸, wherein any two adjacent R⁸ optionally combine toform a ring, which is optionally substituted one or more times withsubstituents selected independently from R^(x). In some embodiments ofany of the aforementioned embodiments, R⁴ is pyrrol-1-yl orimidazol-1-yl, each of which is optionally substituted one or more timeswith substituents selected independently from R⁸, wherein any twoadjacent R⁸ optionally combine to form a ring, which is optionallysubstituted one or more times with substituents selected independentlyfrom R^(x). In some further embodiments of any of the aforementionedembodiments, R⁴ is pyrrol-1-yl or imidazol-1-yl, each of which isoptionally substituted one or more times with substituents selectedindependently from the group consisting of a C₁₋₆ alkyl, C₂₋₆ alkenyl,and phenyl, or any two adjacent substituents can optionally combine toform a —(CH)₄— ring. In some further embodiments of any of theaforementioned embodiments, R⁴ is pyrrol-1-yl, which is optionallysubstituted (e.g., at the 2 and 5 positions) with one or moresubstituents selected independently from the group consisting of C₁₋₆alkyl (e.g., methyl) and phenyl. In some further embodiments of any ofthe aforementioned embodiments, R⁴ is imidazol-1-yl, which is optionallysubstituted (e.g., at the 2 and 5 positions) with one or moresubstituents selected independently from the group consisting of C₁₋₆alkyl (e.g., methyl) and phenyl. In some further embodiments of any ofthe aforementioned embodiments, R⁴ is indol-1-yl, which is optionallysubstituted (e.g., at the 2 position) with one or more substituentsselected independently from the group consisting of C₁₋₆ alkyl (e.g.,methyl) and phenyl. In some further embodiments of any of theaforementioned embodiments, R⁴ is indol-1-yl, which is optionallysubstituted (e.g., at the 2 position) with —O—C₁₋₆ alkyl (e.g., —O—CH₃).In some embodiments of any of the aforementioned embodiments, R⁴ ispyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, 2,5-diphenylpyrrol-1-yl,2,5-dimethylimidazol-1-yl, or indol-1-yl.

In any of the above aspects and embodiments, the compounds can includeone or more stereocenters, and may undergo isomerization (e.g., syn-antiisomerization). The disclosure covers any such stereoisomers and otherisomers.

In one or more further aspects, the disclosure provides compounds ofFormula (II)

wherein:

M is a molybdenum atom or a tungsten atom;

R¹⁰¹ is aryl, heteroaryl, alkyl, or cycloalkyl, each of which isoptionally substituted;

R¹⁰² is pyrrolyl, imidazolyl, indolyl, pyrazolyl, azaindolyl, orindazolyl, each of which is optionally substituted; or R¹⁰² is—O—Si(phenyl)₃ when R¹⁰³ is —Si(phenyl)₃, the phenyl groups beingoptionally substituted;

R¹⁰³ is C₁₋₆ alkyl, C₁₋₆ heteroalkyl, aryl, or heteroaryl, each of whichis optionally substituted; or R¹⁰³ is tert-butyl, —C(CH₃)₂(CF₃),—C(CF₃)₃, or —C(CF₃)₂-(phenyl); or R¹⁰³ is —Si(phenyl)₃ when R¹⁰² is—O—Si(phenyl)₃, the phenyl groups being optionally substituted;

R¹⁰⁴ is a hydrogen atom, C₁₋₆ alkyl, or alkoxy;

R¹⁰⁵ is a hydrogen atom, —O—(C₁₋₆ alkyl), —CH₂—O—(C₁₋₆ alkyl),heteroalkoxy, or —N(C₁₋₆ alkyl)₂;

R¹⁰⁶ and R¹⁰⁷ are independently a hydrogen atom, C₁₋₆ alkyl, C₁₋₆alkoxy, a halogen atom, —NO₂, amides, or sulfonamides.

In some further embodiments of any of the aforementioned aspects andembodiments, R¹⁰¹ is phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl,2,6-diisopropylphenyl, 2-trifluoromethylphenyl, pentafluorophenyl,tert-butyl, or 1-adamantyl.

In some further embodiments of any of the aforementioned aspects andembodiments, R¹⁰² is pyrrolyl, imidazolyl, or indolyl, each of which isoptionally substituted. In some further embodiments, R¹⁰² ispyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, 2,5-diphenylpyrrol-1-yl,2,5-dimethylimidazol-1-yl, or indol-1-yl.

In some further embodiments of any of the aforementioned aspects andembodiments, R¹⁰³ is 2,6-diphenylphenyl,4-bromo-2,3,5,6-tetraphenylphenyl, tert-butyl, —C(CH₃)₂CF₃, C(CF₃)₃, or—C(CF₃)₂(phenyl). In some other embodiments R¹⁰³ is:

wherein “iPr” refers to isopropyl, and “OTBDMS” refers totert-butyldimethylsilyloxy.

In some further embodiments of any of the aforementioned aspects andembodiments, R¹⁰⁴ is a hydrogen atom.

In some further embodiments of any of the aforementioned aspects andembodiments, R¹⁰⁵ is a hydrogen atom, methyloxy, ethyloxy,methyloxymethyloxy, isopropyloxy, or dimethylamino.

In some further embodiments of any of the aforementioned aspects andembodiments, R¹⁰⁶ and R¹⁰⁷ are independently a hydrogen atom, C₁₋₆alkyl, C₁₋₆ alkoxy, or a halogen atom. In some further embodiments, R¹⁰⁶and R¹⁰⁷ are independently a hydrogen atom, methyl, a halogen atom, ormethyloxy.

In any of the above aspects and embodiments, the compounds can includeone or more stereocenters, and may undergo isomerization (e.g., syn-antiisomerization). The disclosure covers any such stereoisomers and otherisomers.

In some further aspects, compounds of any of the aforementioned aspectsand embodiments can be illustrated by reference to specific compounds.Table 2 below provides a list of 62 compounds that illustrate compoundsthat are encompassed by one or more of the aforementioned aspects andembodiments. The compounds of Table 2 can be understood in terms of thegeneric structure of Formula (III) and the definitions of Tables 1A-1D.

TABLE 1A Chemical Moiety Moiety Number 2,6-Dimethylphenyl A-12,6-Diisopropylphenyl A-2 2,6-Dichlorophenyl A-3 1-Adamantyl A-4Pentafluorophenyl A-5

TABLE 1B Chemical Moiety Moiety Number Pyrrol-1-yl B-12,5-Dimethylpyrrol-1-yl B-2 Triphenylsilyloxy B-3 —O—C(CF₃)₃ B-4—O—C(CH₃)(CF₃)₂ B-5 —O—C(CH₃)₂(CF₃) B-6 2-Ethoxy-indol-1-yl B-7—O—C(CH₃)₂—CH₂—O—CH₃ B-8

TABLE 1C Chemical Moiety Moiety Number 2,6-Diphenylphenyl C-14-Bromo-2,3,5,6-tetraphenylphenyl C-2 Triphenylsilyl C-3

C-4

C-5

C-6

C-7 4-Nitro-2,3,5,6-tetraphenylphenyl C-8 —C(CH₃)(CF₃)₂ C-92,3,5,6-Tetraphenylphenyl  C-10 In the above table, “OTBDMS” istert-butyldimethylsilyloxy.

TABLE 1D Chemical Moiety Moiety Number 2-Methoxyphenyl D-14-Fluoro-2-methoxyphenyl D-2 5-Fluoro-2-methoxyphenyl D-32,4-Dimethoxyphenyl D-4 2,5-Dimethoxyphenyl D-5 2-Methoxy-4-methylphenylD-6 2-Methoxy-5-methylphenyl D-7 Phenyl D-8 2,4,5-Trimethoxyphenyl D-92-Ethoxyphenyl D-10 2-Isopropoxyphenyl D-11 2-(Methoxymethyl)phenyl D-122-(Dimethylamino)phenyl D-13 2-Pyridyl (i.e., Pyridin-2-yl) D-14—O-(tetrahydropyran-2-yl) D-15 —O—(C═O)—CH₃ D-16 —O—(C═O)—C(CH₃)₃ D-17—O—(C═O)-(phenyl) D-18 2-Methoxy-4-nitrophenyl D-19 Pyrrolidin-2-on-1-ylD-20 2-Methoxy-pyridin-3-yl D-21

TABLE 2 Compound M R²⁰¹ R²⁰² R²⁰³ R²⁰⁴ R²⁰⁵ 1 Mo A-1 B-2 C-1 H D-1 2 WA-3 B-2 C-4 H D-1 3 W A-3 B-2 C-2 H D-1 4 Mo A-2 B-2 C-2 H D-1 5 W A-3B-2 C-4 H D-2 6 W A-3 B-2 C-4 H D-3 7 W A-3 B-2 C-6 H D-1 8 W A-3 B-2C-4 H D-5 9 W A-3 B-2 C-4 H D-4 10 W A-3 B-2 C-4 H D-8 11 W A-3 B-2 C-4H D-6 12 W A-3 B-2 C-4 H D-7 13 W A-3 B-2 C-4 H D-9 14 W A-3 B-2 C-7 HD-1 15 W A-3 B-2 C-4 H D-10 16 W A-3 B-2 C-4 H D-11 17 W A-3 B-2 C-4 HD-12 18 Mo A-1 B-2 C-4 H D-1 19 Mo A-2 B-2 C-4 H D-1 20 W A-3 B-2 C-4 HD-13 21 Mo A-2 B-2 C-1 H D-1 22 W A-3 B-2 C-5 H D-1 23 Mo A-4 B-2 C-4 HD-1 24 Mo A-4 B-2 C-5 H D-1 25 Mo A-1 B-2 C-5 H D-1 26 Mo A-2 B-2 C-5 HD-1 27 W A-1 B-2 C-4 H D-1 28 W A-3 B-2 C-2 H D-2 29 W A-3 B-2 C-2 H D-430 W A-3 B-2 C-2 H D-6 31 W A-3 B-2 C-2 H D-12 32 W A-3 B-2 C-2 H D-1333 Mo A-2 B-3 C-3 H D-1 34 W A-2 B-3 C-3 H D-1 35 W A-3 B-2 C-2 H D-1436 Mo A-2 B-2 C-2 H D-14 37 Mo A-2 B-5 C-2 H D-1 38 Mo A-2 B-4 C-2 H D-139 Mo A-2 B-6 C-2 H D-1 40 Mo A-2 B-2 C-2 H D-15 41 Mo A-2 B-7 C-2 H D-142 W A-3 B-6 C-2 H D-1 43 W A-3 B-5 C-2 H D-1 44 W A-3 B-4 C-2 H D-1 45Mo A-2 B-2 C-4 H D-15 46 W A-2 B-7 C-2 H D-1 47 Mo A-2 B-7 C-9 H D-1 48W A-3 B-8 C-2 H D-1 49 W A-3 B-7 C-2 H D-1 50 Mo A-2 B-2 C-2 H D-16 51 WA-2 B-2 C-2 H D-1 52 Mo A-2 B-2 C-2 H D-17 53 W A-5 B-2 C-4 H D-1 54 MoA-2 B-2 C-2 H D-18 55 Mo A-2 B-2 C-2 H D-19 56 W A-3 B-2 C-2 H D-19 57Mo A-2 B-2 C-8 H D-1 58 W A-3 B-2 C-8 H D-1 59 W A-3 B-2 C-10 H D-1 60Mo A-2 B-2 C-2 H D-15 61 Mo A-2 B-2 C-2 H D-20 62 W A-3 B-2 C-2 H D-2063 Mo A-2 B-2 C-2 H D-21 64 W A-3 B-2 C-2 H D-21

Compound Preparation

The compounds disclosed in any of the aforementioned aspects andembodiments, including the compounds in Table 2, may be prepared bymethods known in the art using commercially available materials andart-recognized methods. Illustrative synthetic methods are recited belowin the Examples. The ordinarily skilled artisan may use these examplesas a guide and thereby prepare other compounds in an analogous mannerusing ordinary skill in the art.

Methods of Use

The compounds disclosed in any of the aforementioned aspects andembodiments, including the compounds in Table 2, may be used to catalyzeolefin metathesis reactions of various kinds. The terms “metathesis” or“metathesizing” can refer to a variety of different reactions,including, but not limited to, cross-metathesis, self-metathesis,ring-opening metathesis, ring-opening metathesis polymerizations(“ROMP”), ring-closing metathesis (“RCM”), and acyclic diene metathesis(“ADMET”). Any suitable metathesis reaction can be catalyzed by thecompounds disclosed herein. Therefore, the compounds disclosed hereincan be suitable used for making various compounds that may otherwise bedifficult to make, including, but not limited to, pharmaceuticalcompounds, agrochemical compounds, flavor compounds, and fragrancecompounds.

In certain aspects, the disclosure provides methods of carrying out ametathesis reaction, including: providing a first compound having one ormore carbon-carbon double bonds; and reacting the first compound via ametathesis reaction in the presence of a metathesis catalyst, such as acompound of any of the aforementioned aspects and embodiments.

In some embodiments, the first compound has two or more carbon-carbondouble bonds. In some such embodiments, the metathesis reaction is aring-closing metathesis reaction between two of the two or morecarbon-carbon double bonds of the first compound. In some suchembodiments, a catalytically effective amount of the metathesis catalystis present. The catalytically effective amount can vary depending on thenature of the reaction being catalyzed and the desired product.

In some other aspects, the disclosure provides methods of carrying out ametathesis reaction, including: providing a first compound having one ormore carbon-carbon double bond and a second compound having one or morecarbon-carbon double bonds; and reacting the first compound and thesecond compound via a metathesis reaction in the presence of ametathesis catalyst, such as a compound of the first or second aspectsdisclosed herein.

In some embodiments, the first compound and the second compound are thesame compound, meaning that the reaction is a self-metathesis reaction.In some other embodiments, the first compound and the second compoundare not the same, meaning that it is a cross-metathesis reaction.

In some such embodiments, the first compound is an internal olefin, suchas a natural oil. In some embodiments, the second compound is ashort-chain alkene, such as ethylene. In some such embodiments, themetathesis reaction yields an amount of 9-decenoic acid or an ester orcarboxylate salt thereof.

Any suitable catalyst loadings can be used for the metathesis reactions.For example, in some embodiments, the catalyst loading relative to themetathesis substrate (e.g., a natural oil triglyceride) is no more than2000 molar ppm, or no more than 1500 molar ppm, or no more than 1000molar ppm, or no more than 500 molar ppm, or no more than 350 molar ppm,or no more than 200 molar ppm, or no more than 175 molar ppm, or no morethan 140 molar ppm, or no more than 100 molar ppm, or no more than 70molar ppm. In some embodiments, the catalyst loading relative to themetathesis substrate (e.g., a natural oil triglyceride) is from 15 to2000 molar ppm, or from 15 to 1000 molar ppm, or from 25 to 500 molarppm, or from 35 to 350 molar ppm, or from 35 to 200 molar ppm, or from35 to 175 molar ppm, or from 35 to 200 molar ppm.

Metathesis of Natural Oils

In some embodiments, the compounds disclosed in the aforementionedaspects and embodiments can be suitable used to metathesize naturaloils, e.g., as glycerides, as alkyl esters (e.g., methyl esters), etc.Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst (such as thosedisclosed herein), some or all of the original carbon-carbon doublebonds are broken, and new carbon-carbon double bonds are formed. Theproducts of such metathesis reactions include carbon-carbon double bondsin different locations, which can provide unsaturated organic compoundshaving useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

Metathesized natural oils can also be used. Examples of metathesizednatural oils include but are not limited to a metathesized vegetableoil, a metathesized algal oil, a metathesized animal fat, a metathesizedtall oil, a metathesized derivatives of these oils, or mixtures thereof.For example, a metathesized vegetable oil may include metathesizedcanola oil, metathesized rapeseed oil, metathesized coconut oil,metathesized corn oil, metathesized cottonseed oil, metathesized oliveoil, metathesized palm oil, metathesized peanut oil, metathesizedsafflower oil, metathesized sesame oil, metathesized soybean oil,metathesized sunflower oil, metathesized linseed oil, metathesized palmkernel oil, metathesized tung oil, metathesized jatropha oil,metathesized mustard oil, metathesized camelina oil, metathesizedpennycress oil, metathesized castor oil, metathesized derivatives ofthese oils, or mixtures thereof. In another example, the metathesizednatural oil may include a metathesized animal fat, such as metathesizedlard, metathesized tallow, metathesized poultry fat, metathesized fishoil, metathesized derivatives of these oils, or mixtures thereof.

Such natural oils, or derivatives thereof, can contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain olefins, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene and 1-decenoid acid (or an esterthereof), among other products, are formed. Followingtransesterification, for example, with an alkyl alcohol, an amount of9-denenoic acid alkyl ester is formed. In some such embodiments, aseparation step may occur between the metathesis and thetransesterification, where the alkenes are separated from the esters. Insome other embodiments, transesterification can occur before metathesis,and the metathesis is performed on the transesterified product.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication Nos. 2011/0113679,2014/0275681, and 2014/0275595, all three of which are herebyincorporated by reference as though fully set forth herein.

For example, in some embodiments, the metathesis substrate materials tobe subjected to metathesis reactions using the compounds disclosedherein are purified from impurities that may poison the catalytic effectof the compounds. Suitable methods include, but are not limited to,percolation through molecular sieves to remove water (or reduce watercontent to the acceptable level), optionally followed by a furtherpercolation through activated alumina to remove/cleave organic peroxideand eliminate other impurities (e.g. alcohols, aldehydes, ketones). Insome embodiments, distillation from sodium and/or potassium (e.g.styrene) may be sufficient to obtain suitably pure substrates.Similarly, when the water content is not high (e.g., less than about 250ppm, relative to the concentration of the metathesis substratematerial), percolation through alumina may be sufficient. A typicalcommercially-available alumina is SELEXSORB (BASF, Leverkusen, Germany).This is an activated alumina-based adsorbent containing a proprietarymodifier, and is used as an industrial adsorbent.

In some other embodiments, olefin feedstocks are used withoutpurification, e.g., if trialkylaluminum (e.g. triethylaluminum) is addedto the metathesis reaction. In such instances, trialkylaluminum may beused as an additive, e.g., in an amount of 0.5-5.0 mol %, relative tothe concentration of the metathesis substrate material. Using thismethod or a combination of trialkylaluminum with molecular sieves and/oralumina may provide <10 ppm water content and, in some cases, theperoxide content is reduced, e.g., to below its detection limit.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin (or short-chainolefin) is in the C₂₋₆ range. As a non-limiting example, in oneembodiment, the low-molecular-weight olefin may comprise at least oneof: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene,3-methyl-1-butene, cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene,3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. In someembodiments, the short-chain olefin is 1-butene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, the unsaturatedesters may be derived from a natural oil feedstock, in addition to othervaluable compositions. Moreover, in some embodiments, a number ofvaluable compositions can be targeted through the self-metathesisreaction of a natural oil feedstock, or the cross-metathesis reaction ofthe natural oil feedstock with a low-molecular-weight olefin ormid-weight olefin, in the presence of a metathesis catalyst. Suchvaluable compositions can include fuel compositions, detergents,surfactants, and other specialty chemicals. Additionally,transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, multiple metathesis reactions can also beemployed. In some embodiments, the multiple metathesis reactions occursequentially in the same reactor. For example, a glyceride containinglinoleic acid can be metathesized with a terminal lower alkene (e.g.,ethylene, propylene, 1-butene, and the like) to form 1,4-decadiene,which can be metathesized a second time with a terminal lower alkene toform 1,4-pentadiene. In other embodiments, however, the multiplemetathesis reactions are not sequential, such that at least one otherstep (e.g., transesterification, hydrogenation, etc.) can be performedbetween the first metathesis step and the following metathesis step.These multiple metathesis procedures can be used to obtain products thatmay not be readily obtainable from a single metathesis reaction usingavailable starting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

For example, multiple metathesis can be employed to make the dibasicacid compounds used to make the diesters disclosed herein. In someembodiments, alkyl (e.g., methyl) esters of 9-decenoic acid,9-undecenoic acid, 9-dodecenoic acid, or any combination thereof, can bereacted in a self-metathesis reaction or a cross-metathesis to generatevarious unsaturated dibasic alkyl esters, such as dimethyl9-octadecendioate. Such compounds can then be converted to dibasic acidsby hydrolysis or via saponification followed by acidification. If asaturated dibasic acid is desired, the compound can be hydrogenated,either before conversion to the acid or after. Dibasic acids of otherchain lengths can be made by analogous means. The conditions for suchmetathesis reactions, and the reactor design, and suitable catalysts areas described below with reference to the metathesis of the olefinesters. That discussion is incorporated by reference as though fully setforth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin is in the C₂₋₆range. As a non-limiting example, in one embodiment, thelow-molecular-weight olefin may comprise at least one of: ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, terminal olefinsand internal olefins may be derived from a natural oil feedstock, inaddition to other valuable compositions. Moreover, in some embodiments,a number of valuable compositions can be targeted through theself-metathesis reaction of a natural oil feedstock, or thecross-metathesis reaction of the natural oil feedstock with alow-molecular-weight olefin or mid-weight olefin, in the presence of ametathesis catalyst. Such valuable compositions can include fuelcompositions, detergents, surfactants, and other specialty chemicals.Additionally, transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, the methods disclosed herein can employmultiple metathesis reactions. In some embodiments, the multiplemetathesis reactions occur sequentially in the same reactor. Forexample, a glyceride containing linoleic acid can be metathesized with aterminal lower alkene (e.g., ethylene, propylene, 1-butene, and thelike) to form 1,4-decadiene, which can be metathesized a second timewith a terminal lower alkene to form 1,4-pentadiene. In otherembodiments, however, the multiple metathesis reactions are notsequential, such that at least one other step (e.g.,transesterification, hydrogenation, etc.) can be performed between thefirst metathesis step and the following metathesis step. These multiplemetathesis procedures can be used to obtain products that may not bereadily obtainable from a single metathesis reaction using availablestarting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments wherea reagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gasesinclude helium, neon, argon, and nitrogen, used individually or in witheach other and other inert gases.

The reactor design for the metathesis reaction can vary depending on avariety of factors, including, but not limited to, the scale of thereaction, the reaction conditions (heat, pressure, etc.), the identityof the catalyst, the identity of the materials being reacted in thereactor, and the nature of the feedstock being employed. Suitablereactors can be designed by those of skill in the art, depending on therelevant factors, and incorporated into a refining process such, such asthose disclosed herein.

In certain embodiments, the metathesis catalyst (such as the compoundsdisclosed herein) is dissolved in a solvent prior to conducting themetathesis reaction. In certain such embodiments, the solvent chosen maybe selected to be substantially inert with respect to the metathesiscatalyst. For example, substantially inert solvents include, withoutlimitation: aromatic hydrocarbons, such as benzene, toluene, xylenes,etc.; halogenated aromatic hydrocarbons, such as chlorobenzene anddichlorobenzene; aliphatic solvents, including pentane, hexane, heptane,cyclohexane, etc.; and chlorinated alkanes, such as dichloromethane,chloroform, dichloroethane, etc. In some embodiments, the solventcomprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than −40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

The metathesis reaction can be run under any desired pressure. In someinstances, it may be desirable to maintain a total pressure that is highenough to keep the cross-metathesis reagent in solution. Therefore, asthe molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than 0.1 atm (10 kPa), or greater than 0.3 atm (30 kPa),or greater than 1 atm (100 kPa). In some embodiments, the reactionpressure is no more than about 70 atm (7000 kPa), or no more than about30 atm (3000 kPa). In some embodiments, the pressure for the metathesisreaction ranges from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

Examples General Procedures

The following general procedures were used to make the compoundsdisclosed in Table 2. All complexes were handled in a glovebox under anitrogen (N₂) atmosphere. Benzene and 1,2-dimethoxyethane were distilledfrom sodium or potassium and stored on activated molecular sieves in anitrogen-filled glovebox. Then, n-Pentane was washed with sulfuric acid,followed by water and saturated aqueous solution of sodiumhydrogencarbonate, dried over calcium chloride pellets, and distilledfrom potassium. Benzene-d₆ was dried over activated molecular sieves.

All ¹H-NMR spectra were recorded using a Varian Mercury (200 MHz) orBruker Avance (300 MHz) spectrometer. Chemical shifts were reported inppm from tetramethylsilane with the solvent resonance resulting fromincomplete deuteration as the internal reference (C₆D₆: δ 7.16, CDCl₃: δ7.24). Data were reported as follows: chemical shift, integration,multiplicity (s=singlet, d=doublet, t=triplet, br=broad, m=multiplet),coupling constants (Hz). GC spectra were performed on a Shimadzu GC-2010Plus, and MS spectra were recorded on a GCMS-QP 2010 Ultra.

The compounds were made in a manner consistent with the experimentalprocedures set forth in the following references: (1) T. Kreickmann etal., Organometallics, 2007, 5702-5711 (and references cited therein);(2) L. Gerber et al., Organometallics, 2013, 2373-2378; (3) R. Singh etal., Organometallics, 2007, 2528-2539; (4) U.S. Pat. No. 8,362,311; (5)A. S. Hock et al., J. A. Chem. Soc., 2006, 16373-16375; (6) S. C.Martinescu, Organometallics, 2008, 6570-6578; (7) P. Wipf et al. J. Org.Chem., 2001, 3133-3139; (8) Bellera M. et al., Tetrahedron, 2008,1316-1322; (9) Masahiro M. et al. Angew. Chem. Int. Ed., 1997,1740-1742; and (10) D. H. Hua et al., Tetrahedron Asymmetry, 2001,1999-2004.

In some instances, reagents used to make the catalysts were passedthrough activated alumina before use. For example, oct-1-ene,allylbenzene, and diethyl diallylmalonate were passed through activatedalumina and stored on activated molecular sieves in a nitrogen-filledglovebox prior to use.

Synthesis of Intermediate Compounds

Intermediates used to make the compounds disclosed herein were preparedby the following procedures.

Synthesis of 4-fluoro-1-methoxy-2-vinylbenzene. A suspension of 12.73 gof methyl triphenylphosphonium bromide in 100 mL of dry THF was treatedat room temperature with 15.6 mL of n-butyl lithium (n-BuLi) (2.5 Msolution in n-hexane). The resulting orange solution was stirred for 4hours. Then, a solution of 5.00 g of 5-fluoro-2-methoxybenzaldehyde in25 mL of dry tetrahydrofuran (THF) was added dropwise. Upon addition, awhite precipitate formed. The suspension was stirred for 1 hour andconcentrated in vacuo to give a viscous orange oil that was purified bypassing it through a short column of SiO₂ (heptane), then vacuumdistilled to yield 525 mg of 4-fluoro-1-methoxy-2-vinylbenzene as acolorless liquid. ¹H-NMR (300 MHz, CDCl₃): δ 3.75 (s, 3H), 5.23 (dd,J₁=11.1 Hz, J₂=1.5 Hz, 1H), 5.64 (dd, J₁=17.7 Hz, J₂=1.5 Hz, 1H),6.69-6.74 (m, 1H), 6.81-6.98 (m, 1H), 7.07-7.12 (m, 1H). GC-MS: 97.0% MS(EI): 152.

Synthesis of 4-fluoro-2-methoxy-1-vinylbenzene. A suspension of 12.73 gof methyl triphenylphosphonium bromide in 100 mL of dry THF was treatedat room temperature with 15.6 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 hours. Then, a solutionof 5.00 g of 4-fluoro-o-anisaldehyde in 25 mL of dry THF was addeddropwise. Upon addition a white precipitate formed. The suspension wasstirred for 1 hour and concentrated in vacuo to give a viscous orangeoil that was purified by passing through a short column of SiO₂(heptane) then vacuum distillation to yield 321 mg of4-fluoro-2-methoxy-1-vinylbenzene as a colorless liquid. ¹H-NMR (300MHz, CDCl₃): δ 3.76 (s, 3H), 5.15 (dd, J₁=11.1 Hz, J₂=1.4 Hz, 1H), 5.69(dd, J₁=17.6 Hz, J₂=1.4 Hz, 1H), 6.48-6.60 (m, 2H), 6.81-6.94 (m, 1H),7.29-7.37 (m, 1H). GC-MS: 97.5% MS (EI): 152.

Synthesis of 1,4-dimethoxy-2-vinylbenzene. A suspension of 11.71 g ofmethyl triphenylphosphonium bromide in 100 mL of dry THF was treated atroom temperature with 14.3 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 hours. Then, a solutionof 5.00 g of 2,5-dimethoxybenzaldehyde in 25 mL of dry THF was addeddropwise. Upon addition, a white precipitate formed. The suspension wasstirred for 1 hour and concentrated in vacuo to give a viscous orangeoil that was purified by passing through a short column of SiO₂(heptane) then vacuum distillation to yield 1.92 g of1,4-dimethoxy-2-vinylbenzene as a colorless liquid. ¹H-NMR (300 MHz,CDCl₃): δ 3.71 (s, 3H), 3.73 (s, 3H), 5.19 (dd, J₁=11.2 Hz, J₂=1.6 Hz,1H), 5.64 (dd, J₁=17.7 Hz, J₂=1.6 Hz, 1H), 6.68-6.75 (m, 2H), 6.90-6.99(m, 2H). GC-MS: 98.0% MS (EI): 164.

Synthesis of 2,4-dimethoxy-1-vinylbenzene. A suspension of 11.59 g ofmethyl triphenylphosphonium bromide in 100 mL of dry THF was treated atroom temperature with 14.2 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 hour. Then, a solutionof 5.00 g of 2,4-dimethoxybenzaldehyde in 25 mL of dry THF was addeddropwise. Upon addition, a white precipitate formed. The suspension wasstirred for 1 hour and concentrated in vacuo to give a viscous orangeoil that was purified by passing through a short column of SiO₂(heptane) then vacuum distillation to yield 1.96 g of2,4-dimethoxy-1-vinylbenzene as a colorless liquid. ¹H-NMR (300 MHz,CDCl₃): δ 3.74 (s, 3H), 3.75 (s, 3H), 5.06 (dd, J₁=11.2 Hz, J₂=1.5 Hz,1H), 5.55 (dd, J₁=17.7 Hz, J₂=1.5 Hz, 1H), 6.34-6.43 (m, 2H), 6.80-6.94(m, 1H), 7.31 (d, J=8.4 Hz, 1H). GC-MS: 95.6% MS (EI): 164.

Synthesis of 1-methoxy-4-methyl-2-vinylbenzene. A suspension of 8.68 gof methyl triphenylphosphonium bromide in 60 mL of dry THF was treatedat room temperature with 10.6 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 hours. Then, a solutionof 3.32 g of 2-methoxy-5-methyl-benzaldehyde in 25 mL of dry THF wasadded dropwise. Upon addition, a white precipitate formed. Thesuspension was stirred for 1 hour and concentrated in vacuo to give aviscous yellow oil that was purified by passing through a short columnof SiO₂ (heptane) then vacuum distillation to yield 765 mg of1-methoxy-4-methyl-2-vinylbenzene as a colorless liquid. ¹H-NMR (300MHz, CDCl₃): δ 2.22 (s, 3H), 3.75 (s, 3H), 5.17 (dd, J₁=11.1 Hz, J₂=1.4Hz, 1H), 5.64 (dd, J₁=17.8 Hz, J₂=1.4 Hz, 1H), 6.69 (d, J=8.3 Hz, 1H),6.86-7.01 (m, 2H), 7.17 (d, J=8.0 Hz, 1H). GC-MS: 98.4% MS (EI): 148.

Synthesis of 2-methoxy-4-methyl-1-vinylbenzene. A suspension of 13.08 gof methyl triphenylphosphonium bromide in 75 mL of dry THF was treatedat room temperature with 16.0 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 hour. Then, a solutionof 5.00 g of 2-methoxy-4-methyl-benzaldehyde in 25 mL of dry THF wasadded dropwise. Upon addition, a white precipitate formed. Thesuspension was stirred for 1 hour and concentrated in vacuo to give aviscous yellow oil that was purified by passing through a short columnof SiO₂ (heptane) then vacuum distillation to yield 1.46 g of2-methoxy-4-methyl-1-vinylbenzene as a colorless liquid. ¹H-NMR (300MHz, CDCl₃): δ 2.27 (s, 3H), 3.76 (s, 3H), 5.13 (dd, J₁=11.2 Hz, J₂=1.5Hz, 1H), 5.61 (dd, J₁=17.7 Hz, J₂=1.5 Hz, 1H), 6.61 (s, 1H), 6.67 (m,1H), 6.93 (m, 1H), 7.28 (d, J=7.7 Hz, 1H). GC-MS: 97.8% MS (EI): 148.

Synthesis of 1,2,4-trimethoxy-5-vinylbenzene. A suspension of 10.02 g ofmethyl triphenylphosphonium bromide in 75 mL of dry THF was treated atroom temperature with 12.2 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 h. Then, a solution of5.00 g (25.5 mmol) of 2,4,5-trimethoxy-benzaldehyde in 25 mL of dry THFwas added dropwise. Upon addition, a white precipitate formed. Thesuspension was stirred for 1 hour and concentrated in vacuo to give aviscous yellow oil that was purified by passing through a short columnof SiO₂ (heptane) then vacuum distillation to yield 1.71 g of1,2,4-trimethoxy-5-vinylbenzene as a colorless liquid. ¹H-NMR (300 MHz,CDCl₃): δ 3.76 (s, 3H), 3.80 (s, 3H), 3.83 (s, 3H), 5.09 (dd, J₁=11.1Hz, J₂=1.4 Hz, 1H), 5.52 (dd, J₁=17.7 Hz, J₂=1.4 Hz, 1H), 6.44 (s, 1H),6.86-6.98 (m, 2H). GC-MS: 95.1% MS (EI): 194.

Synthesis of 1-ethoxy-2-vinylbenzene. A suspension of 14.28 g of methyltriphenylphosphonium bromide in 80 mL of dry THF was treated at roomtemperature with 17.3 mL of n-BuLi (2.5 M solution in n-hexane). Theresulting orange solution was stirred for 4 hours. Then, a solution of5.00 g of 2-ethoxybenzaldehyde in 25 mL of dry THF was added dropwise.Upon addition a white precipitate formed. The suspension was stirred for1 hour and concentrated in vacuo to give a viscous yellow oil that waspurified by passing through a short column of SiO₂ (heptane) then vacuumdistillation to yield 2.86 g of 1-ethoxy-2-vinylbenzene as a colorlessliquid. ¹H-NMR (300 MHz, CDCl₃): δ 1.37 (t, J=7.0 Hz, 3H), 3.98 (q,J=7.0 Hz, 2H), 5.17 (dd, J₁=11.2 Hz, J₂=1.6 Hz, 1H), 5.68 (dd, J₁=17.8Hz, J₂=1.6 Hz, 1H), 6.74-6.89 (m, 2H), 6.94-7.08 (m, 1H), 7.08-7.18 (m,1H), 7.39 (dd, J₁=7.6 Hz, J₂=1.7 Hz, 1H). GC-MS: 98.5% MS (EI): 148.

Synthesis of 1-isopropoxy-2-vinylbenzene. A suspension of 15.65 g ofmethyl triphenylphosphonium bromide in 100 mL of dry THF was treated atroom temperature with 19.0 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 hours. Then, a solutionof 6.00 g (36.5 mmol) of 2-isopropoxybenzaldehyde in 25 mL of dry THFwas added dropwise. Upon addition, a white precipitate formed. Thesuspension was stirred for 1 hour and concentrated in vacuo to give aviscous yellow oil that was purified by passing through a short columnof SiO₂ (heptane) then vacuum distillation to yield 3.66 g of1-isopropoxy-2-vinylbenzene as a colorless liquid. ¹H-NMR (300 MHz,CDCl₃): δ 1.27 (d, J=6.1 Hz, 6H), 4.47 (m, 1H), 5.15 (dd, J₁=11.2 Hz,J₂=1.6 Hz, 1H), 5.65 (dd, J₁=17.8 Hz, J₂=1.6 Hz, 1H), 6.78-6.88 (m, 2H),6.92-7.05 (m, 1H), 7.08-7.16 (m, 1H), 7.40 (dd, J₁=7.6 Hz, J₂=1.7 Hz,1H). GC-MS: >99.0% MS (EI): 162.

Synthesis of 1-(methoxymethyl)-2-vinylbenzene. A suspension of 6.62 g ofmethyl triphenylphosphonium bromide in 30 mL of dry THF was treated atroom temperature with 8.35 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 hours. Then, a solutionof 1.74 g of 2-(methoxymethyl)-benzaldehyde in 10 mL of dry THF wasadded dropwise. Upon addition, a white precipitate formed. Thesuspension was stirred for 1 hour and concentrated in vacuo to give aviscous yellow oil that was purified by passing through a short columnof SiO₂ (heptane) then vacuum distillation to yield 354 mg of1-(methoxymethyl)-2-vinylbenzene as a colorless liquid. ¹H-NMR (300 MHz,CDCl₃): δ 3.32 (s, 3H), 4.44 (s, 2H), 5.25 (dd, J₁=11.0 Hz, J₂=1.4 Hz,1H), 5.60 (dd, J₁=17.4 Hz, J₂=1.4 Hz, 1H), 6.88-7.00 (m, 1H), 7.12-7.29(m, 3H), 7.46 (dm, J₁=7.0 Hz, 1H). GC-MS: >99.0% MS (EI): 148.

Synthesis of N,N-dimethyl-2-vinylaniline. A suspension of 12.16 g ofmethyl triphenylphosphonium bromide in 80 mL of dry THF was treated atroom temperature with 16.30 mL of n-BuLi (2.5 M solution in n-hexane).The resulting orange solution was stirred for 4 h. Then, a solution of3.39 g (22.7 mmol) of 2-(dimethylamino)-benzaldehyde in 20 mL of dry THFwas added dropwise. Upon addition, a white precipitate formed. Thesuspension was stirred for 1 hour and concentrated in vacuo to give aviscous yellow oil that was purified by passing through a short columnof SiO₂ (heptane) then vacuum distillation to yield 448 mg ofN,N-dimethyl-2-vinylaniline as a colorless liquid. ¹H-NMR (300 MHz,CDCl₃): δ 2.65 (s, 6H), 5.17 (dd, J₁=11.0 Hz, J₂=1.6 Hz, 1H), 5.58 (dd,J₁=17.1 Hz, J₂=1.6 Hz, 1H), 6.86-7.03 (m, 3H), 7.11-7.18 (m, 1H), 7.39(dd, J₁=7.5 Hz, J₂=1.7 Hz, 1H). GC-MS: >99.0% MS (EI): 147.

Synthesis of 2-methoxy-4-nitro-1-vinylbenzene. A suspension of 10.85 gof methyl triphenylphosphonium bromide in 100 mL of dry THF was treatedat room temperature with 13.20 mL of n-BuLi (2.5 M solution inn-hexane). The resulting orange solution was stirred for 4 hours. Then,a solution of 5.00 g of 2-methoxy-4-nitrobenzaldehyde in 50 mL of dryTHF was added dropwise. Upon addition, a white precipitate formed. Thesuspension was stirred for 1 hour and concentrated in vacuo to give aviscous yellow oil that was purified by passing it through a shortcolumn of SiO₂ (heptane) and then vacuum distilling to yield 666 mg of2-methoxy-4-nitro-1-vinylbenzene as a yellow liquid. ¹H-NMR (300 MHz,CDCl₃): δ 3.95 (s, 3H), 5.48 (dd, J₁=12.0 Hz, J₂=1.3 Hz, 1H), 5.90 (dd,J₁=16.0 Hz, J₂=1.4 Hz, 1H), 7.00-7.9 (m, 1H), 7.57 (d, J₁=8.47 Hz, 1H),7.72 (d, J₁=2.15 Hz, 1H), 5.48 (dd, J₁=8.45 Hz, J₂=2.0 Hz, 1H).GC-MS: >99.0% MS (EI): 179.

Synthesis of 4-bromo-2,3,5,6-tetraphenylphenol. Under nitrogenatmosphere to the solution of dibenzyl ketone (84.95 g, 1.0 equiv.) andbenzalacetophenone (84.14 g, 1.0 equiv.) in dry methanol (250-300 mL) asolution of sodium methoxide in methanol (140-150 mL) (prepared from 2.0equiv. of sodium in 140-150 mL dry methanol) was added dropwise over10-15 minutes at room temperature (rt), then the reaction mixture wasstirred at rt for 18-20 hours under inert atmosphere. After the reactionwas completed, the reaction mixture was diluted with water (450-500 mL)and the pH was adjusted to 5-6 by 37% aqueous HCl solution; the whiteprecipitate was filtered off and washed with water. The crude productwas recrystallized from methanol to deliver2,3,5,6-tetraphenylcyclohex-2-enone (147.8 g) as an off-white solid. Ina 3-necked 2-L rounded bottom flask equipped with thermometer, condenserand dropping funnel 2.3 equiv. of bromine (45.95 g, 14.73 mL) wasdissolved in acetic acid (600 mL) as it was heated to 75-80° C. Duringthis time 2,3,5,6-tetraphenyl-cyclohex-2-enone was suspended in 100 mLof acetic acid and it was added to the reaction mixture over 10-minuteperiod. The heating was continued until HBr formation could be detected,then the reaction mixture was cooled to 40-45° C. and it was poured intowater (1-1.5 L) and the yellow precipitate was filtered off, washedconsecutively with water (3×250 mL), n-heptane (3×150 mL) and methanol(2×150 mL) to yield 4-bromo-2,3,5,6-tetraphenylphenol (45.72 g) as anoff-white solid. ¹H-NMR (300 MHz, CDCl₃): δ 4.93 (s, 1H), 6.95-7.20 (m,20H). GC-MS: >99.0% MS (EI): 476, 478.

Synthesis of 4-nitro-2,3,5,6-tetraphenylphenol. To a solution of4-bromo-2,3,5,6-tetraphenylphenol (1.00 g) in acetonitrile (20 mL),silver nitrite (0.48 g) was added and the reaction mixture was refluxedfor 20 hours. After the completion of the reaction, the salt phase wasfiltered off and the organic phase was concentrated. The crude productwas purified by column chromatography (Heptane:EtOAc=7:3) to yield 350mg of 4-nitro-2,3,5,6-tetraphenylphenol as off-white solid. ¹H-NMR (300MHz, DMSO-d₆): δ 7.08-7.22 (m, 20H), 8.53 (s, 1H). GC-MS: >99.0% MS(EI): 443.

Synthesis of(R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-ol.To a solution of(R)-3,3′-dibromo-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diol(60.0 g) and tert-butyldimethylsilyl chloride (26.1 g) indichloromethane (400 mL) was added triethyl amine (17.5 g) dropwise andthe reaction mixture was stirred at room temperature for 16 hours. Aftercompletion of the reaction it was diluted with saturated aqueoussolution of ammonium chloride (ca. 100 mL), the water phase wasextracted with dichloromethane twice. The combined organic phases werewashed with water and brine, dried over MgSO₄ and evaporated. The crudeproduct was recrystallized from methanol to yield(R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-ol(68.9 g) as off-white solid. ¹H-NMR (300 MHz, CDCl₃): δ −0.35 (s, 3H),0.11 (s, 3H), 0.82 (s, 9H), 1.52-1.82 (m, 8H), 1.88-2.08 (m, 2H),2.25-2.51 (m, 2H), 2.64-2.77 (m, 4H), 5.12 (s, 1H), 7.21 (s, 1H), 7.32(s, 1H). GC-MS: >99.0% MS (EI): 564, 566, 568.

Synthesis of(R)-3,3′-dibromo-2′-methoxy-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-ol.To the solution of(R)-3,3′-dibromo-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diol(25.1 g) in acetonitrile (200 ml) potassium carbonate (11.5 g) andiodomethane (9.47 g, 4.15 mL) were added at room temperature and themixture was stirred at the same temperature for 18 hours. After allstarting material had been disappeared from the reaction mixture thesolvent was removed in vacuo, the residue was dissolved in chloroform(150 mL) and washed with water (75 mL) and brine (75 mL), dried overMgSO₄ and evaporated. The crude product was purified by columnchromatography to yield(R)-3,3′-dibromo-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diol(11.4 g, 44%) as off-white solid. ¹H-NMR (300 MHz, CDCl₃): δ 1.12-1.55(m, 8H), 1.90-2.01 (m, 2H), 2.11-2.26 (m, 6H), 3.41 (s, 3H), 4.98 (s,1H), 7.19 (s, 1H), 7.29 (s, 1H). GC-MS: >99.0% MS (EI): 464, 466, 468.

Synthesis of potassium 2-ethoxyindol-1-ide. To a solution of 2-oxindole(1.00 g) in dichloromethane (10 mL), triethyloxonium tetrafluoroborate(1.50 g) was added to the solution and it was refluxed for 20 hours.After completion of the reaction, it was cooled to room temperature andwashed with water (10 mL) and brine (10 mL), dried over MgSO₄ andevaporated. The crude product was recrystallized from heptane. Theoff-white solid was dissolved in tetrahydrofuran (10 mL) and potassiumhydride was added to the reaction mixture portionwise. After theaddition was completed, it was stirred at room temperature for 2 hours,then the solvent was removed in vacuo to produce 750 mg of the potassiumsalt.

Synthetic Preparation of Compounds Disclosed Herein.

The below examples describe the synthesis of certain compounds shown inTable 2. Every compound in Table 2 was synthesized. For those compoundsfor which syntheses are not reported, the compounds were synthesized ina manner analogous to the syntheses set forth below. Each exampleidentifies the compound from Table 2 by “Compound #”. Thus, “Compound 2”refers to the second compound set forth in Table 2. The descriptionsbelow use various abbreviations, which are known to those of skill inthe art, and which have the following meanings.

TBS-Bitet-2-OH refers to

2,6-Cl₂C₆H₃ refers to 2,6-dichlorophenyl.

CHCMe₃ refers to ═CH—C(CH₃)₃.

CHC(Me)₂Ph refers to ═CH—C(phenyl)(CH₃)₂

NC₄(CH₃)₂H₂ refers to 2,5-dimethylpyrrolide.

4Br-TPPOH refers to 4-bromo-2,3,5,6-tetraphenylphenol.

4Br-TPPO refers to 4-bromo-2,3,5,6-tetraphenyloxide.

2,6-i-Pr₂C₆H₃ refers to 2,6-diisopropylphenyl.

OTf refers to —O—C(CF₃)₃.

4NO₂-TPPOH refers to 4-nitro-2,3,5,6-tetraphenylphenol.

Example 1: Synthesis of Compound 2. A solution of TBS-Bitet-2-OH (115mg) in 2 mL benzene was added dropwise to a solution ofW(N-2,6-Cl₂C₆H₃)(CHCMe₃)—(NC₄(CH₃)₂H₂)₂ (135 mg) in benzene (2 mL). Thereaction mixture was stirred at room temperature for 4 hours, and thevolatile materials were removed under vacuum. The residue was dissolvedin DME (1,2-dimethoxyethane) (2 mL) and a solution of1-methoxy-2-vinylbenzene (54.5 mg) in DME (2 mL) was added in oneportion and continued the stirring for further 4 hours. After that thereaction mixture was concentrated in vacuo to provide a deep-red oilfrom which the expected product was crystallized by n-pentane (91 mg).¹H-NMR (200 MHz, C₆D₆): δ −0.25 (s, 3H), 0.24 (s, 3H), 0.88 (s, 9H),1.31-2.49 (m, 20H), 2.99-3.31 (m, 4H), 3.67 (s, 3H), 6.09-6.29 (m, 4H),6.48 (t, J=8.2 Hz, 1H), 6.60-6.73 (m, 2H), 6.78-6.91 (m, 3H), 7.28 (s,1H), 11.27 (s, 1H).

Example 2: Synthesis of Compound 3. A solution ofW(N-2,6-Cl₂C₆H₃)(CHCMe₃)-(NC₄(CH₃)₂H₂)₂ (100 mg) in benzene (2 mL) wasadded to a solution of 4Br-TPPOH (79 mg) in benzene (2 mL). The reactionmixture was stirred at room temperature for 4 hours and the volatilematerials were removed under vacuum. The residue was dissolved in 2 mLDME and a solution of 1-methoxy-2-vinylbenzene (45 mg) in DME (2 mL) wasadded in one portion and continued the stirring for further 4 hours.After that the reaction mixture was concentrated in vacuo to provide ared oil from which the expected product was crystallized by n-pentane(112 mg). ¹H-NMR (200 MHz, C₆D₆): δ 1.87 (s, 6H), 3.21 (s, 3H), 5.88 (s,2H), 6.15-6.30 (m, 2H), 6.42-6.61 (m, 2H), 6.71-7.09 (m, 20H), 11.19 (s,3H).

Example 3: Synthesis of Compound 17. A solution of TBS-Bitet-2-OH (86mg) in 2 mL benzene was added dropwise to a solution ofW(N-2,6-Cl₂C₆H₃)(CHCMe₃)-(NC₄(CH₃)₂H₂)₂ (100 mg) in benzene (2 mL). Thereaction mixture was stirred at room temperature for 4 hours and thevolatile materials were removed under vacuum. The residue was dissolvedin DME (2 mL) and a solution of 1-(methoxymethyl)-2-vinylbenzene (45 mg)in DME (2 mL) was added in one portion and continued the stirring forfurther 4 hours. After that the reaction mixture was concentrated invacuo to provide a deep-red oil from which the expected product wascrystallized by n-pentane (12 mg). ¹H-NMR (200 MHz, C₆D₆): δ −0.12 (s,3H), 0.21 (s, 3H), 0.79 (s, 9H), 1.16-1.64 (m, 10H), 1.85-2.55 (m, 14H),3.19 (s, 3H), 5.99-6.33 (m, 3H), 6.44-6.83 (m, 5H), 7.18-7.35 (m, 3H),11.58 (s, 1H).

Example 4: Synthesis of Compound 20. A solution of TBS-Bitet-2-OH (86mg) in 2 mL benzene was added dropwise to a solution ofW(N-2,6-Cl₂C₆H₃)(CHCMe₃)-(NC₄(CH₃)₂H₂)₂ (100 mg) in benzene (2 mL). Thereaction mixture was stirred at room temperature for 4 hours and thevolatile materials were removed under vacuum. The residue was dissolvedin DME (2 mL) and a solution of 1-(dimethylamino)-2-vinylbenzene (45 mg)in DME (2 mL) was added in one portion and continued the stirring forfurther 4 hours. After that the reaction mixture was concentrated invacuo to provide a deep-red oil from which the expected product wascrystallized by n-pentane (58 mg). ¹H-NMR (200 MHz, C₆D₆): δ −0.14 (s,3H), 0.22 (s, 3H), 0.59 (s, 9H), 0.81 (s, 6H), 1.20-1.56 (m, 10H),2.01-2.59 (m, 6H), 2.98 (s, 6H), 6.01-6.29 (m, 4H), 6.55 (t, J=8.1 Hz,1H), 6.65-7.11 (m, 4H), 7.29 (s, 2H), 11.26 (s, 1H).

Example 5: Synthesis of Compound 16. A solution of TBS-Bitet-2-OH (86mg) in 2 mL benzene was added dropwise to a solution ofW(N-2,6-Cl₂C₆H₃)(CHCMe₃)-(NC₄(CH₃)₂H₂)₂ (100 mg) in benzene (2 mL). Thereaction mixture was stirred at room temperature for 4 hours and thevolatile materials were removed under vacuum. The residue was dissolvedin DME (2 mL) and a solution of 1-(isopropoxy)-2-vinylbenzene (49 mg) inDME (2 mL) was added in one portion and continued the stirring forfurther 4 hours. After that the reaction mixture was concentrated invacuo to provide a deep-red oil from which the expected product wascrystallized by n-pentane (45 mg). ¹H-NMR (200 MHz, C₆D₆): δ −0.10 (s,3H), 0.01 (s, 9H), 0.38 (s, 3H), 0.85 (s, 6H), 1.00-1.60 (m, 16H),1.90-2.60 (m, 6H), 4.93 (m, 1H), 6.04-6.24 (m, 3H), 6.44-6.65 (m, 2H),6.70-6.81 (m, 3H), 6.95 (t, J=7.3 Hz, 1H), 7.22-7.26 (m, 2H), 11.44 (s,1H).

Example 6: Synthesis of Compound 25. A solution of MeO-Bitet-2-OH (87mg) in 2 mL benzene was added dropwise to a solution ofMo(N-2,6-(CH₃)₂C₆H₃)—(CHCMe₂Ph)(NC₄(CH₃)₂H₂)₂ (100 mg) in benzene (2mL). The reaction mixture was stirred at room temperature for 4 hoursand the volatile materials were removed under vacuum. The residue wasdissolved in DME (2 mL) and a solution of 1-methoxy-2-vinylbenzene (50mg) in DME (2 mL) was added in one portion and continued the stirringfor further 4 hours. After that the reaction mixture was concentrated invacuo to provide a deep-red oil from which the expected product wascrystallized by n-pentane (45 mg). ¹H-NMR (200 MHz, C₆D₆) (mixture ofdiastereomers): δ 1.25-1.53 (m, 22H), 1.88-2.56 (m, 30H), 3.41^(x) (s,2.5H), 3.45 (s, 3H), 3.51^(x) (s, 2.5H), 3.53 (s, 3H), 6.13 (s, 3.7H),6.30-7.30 (m, 17H), 12.86 (s, 1H), 13.05^(x) (s, 0.85H).

Example 7: Synthesis of Compound 26. A solution of MeO-Bitet-2-OH (79mg) in 2 mL benzene was added dropwise to a solution ofMo(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)-(NC₄(CH₃)₂H₂)₂ (100 mg) in benzene (2 mL).The reaction mixture was stirred at room temperature for 4 hours and thevolatile materials were removed under vacuum. The residue was dissolvedin DME (2 mL) and a solution of 1-methoxy-2-vinylbenzene (45 mg) in DME(2 mL) was added in one portion and continued the stirring for further 4hours. After that the reaction mixture was concentrated in vacuo toprovide a deep-red oil from which the expected product was crystallizedby n-pentane (40 mg). ¹H-NMR (200 MHz, C₆D₆): δ 1.12 (d, J=6.8 Hz, 6H),1.19 (d, J=6.8 Hz, 6H), 1.28-1.54 (m, 14H), 2.00-2.50 (m, 10H), 3.42 (s,3H), 3.51 (m, 5H), 6.11 (s, 2H), 6.27 (d, J=7.3 Hz, 1H), 6.51 (d, J=7.9Hz, 1H), 6.66-6.86 (m, 3H), 6.89-7.09 (m, 4H), 12.94 (s, 1H).

Example 8: Synthesis of Compound 33. A solution of triphenylsilanol (355mg) in 3 mL benzene was added dropwise to a solution ofMo(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)-(NC₄(CH₃)₂H₂)₂ (328 mg) in benzene (3 mL).The reaction mixture was stirred at room temperature for 4 hours and thevolatile materials were removed under vacuum. The residue was dissolvedin DME (10 mL) and a solution of 1-methoxy-2-vinylbenzene (164 mg) inDME (5 mL) was added in one portion and continued the stirring forfurther 4 hours. After that the reaction mixture was concentrated invacuo to provide a deep-red oil from which the expected product wascrystallized by n-pentane (228 mg). ¹H-NMR (300 MHz, C₆D₆): δ 1.02 (s,6H), 1.04 (s, 6H), 3.08 (s, 3H), 4.09 (m, 2H), 6.04 (d, J=7.8 Hz, 1H),6.42 (d, J=7.9 Hz, 1H), 6.57 (t, J=7.5 Hz, 1H), 6.87 (t, J=7.5 Hz, 1H),6.95-7.12 (m, 21H), 7.65-7.72 (m, 12H), 12.35 (s, 1H).

Example 9: Synthesis of Compound 34. Lithium salt of triphenylsilanol(676 mg) was added to the solution ofW(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)(OTf)₂DME (1.00 g) in toluene (10 mL) at−30° C., and the suspension was stirred at room temperature overnight.After completion of the reaction, it was filtered through a Celite padand the filtrate was concentrated to yield a brown solid. The solidprecipitate was dissolved in DME (5 mL), and a solution of1-methoxy-2-vinylbenzene (306 mg) in DME (5 mL) was added in one portionand continued the stirring for further 4 hours. After that the reactionmixture was concentrated in vacuo to provide a deep-red oil from whichthe product was crystallized in n-pentane (464 mg). 1H-NMR (300 MHz,C₆D₆): δ 1.17 (d, J=6.8 Hz, 6H), 1.26 (d, J=6.8 Hz, 6H), 1.70 (s, 6H),3.86 (m, 2H), 5.54 (d, J=7.8 Hz, 1H), 5.86 (s, 2H), 6.16-6.22 (m, 1H),6.60-7.10 (m, 24H), 7.55 (m, 1H), 11.52 (s, 1H).

Example 10: Synthesis of Compound 35. A solution ofW(N-2,6-Cl₂C₆H₃)(CHCMe₃)-(NC₄(CH₃)₂H₂)₂ (200 mg) in benzene (3 mL) wasadded to a solution of 4Br-TPPOH (166 mg) in benzene (3 mL). Thereaction mixture was stirred at room temperature for 4 hours, and thevolatile materials were removed under vacuum. The residue was dissolvedin 5 mL DME, and a solution of 2-vinylpyridine (105 mg) in DME (2 mL)was added in one portion and continued the stirring for an additional 4hours. After that, the reaction mixture was concentrated in vacuo toprovide a red oil from which the product was crystallized by n-pentane(171 mg). 1H-NMR (300 MHz, C₆D₆): δ 1.96 (s, 6H), 5.53 (d, J=7.8 Hz),5.92 (s, 2H), 6.02 (m, 1H), 6.16 (t, J=8.0 Hz, 1H), 6.55 (m, 1H),6.60-7.05 (m, 20H), 7.60 (m, 1H), 8.06 (s, 1H), 8.48 (m, 1H), 10.53 (s,1H).

Example 11: Synthesis of Compound 36. A solution ofMo(N-2,6-i-Pr₂C₆H₃)—(CHCMe₂Ph)(NC₄(CH₃)₂H₂)₂ (200 mg) in benzene (3 mL)was added to a solution of 4Br-TPPOH (161 mg) in benzene (3 mL). Thereaction mixture was stirred at room temperature for 4 hours and thevolatile materials were removed under vacuum. The residue was dissolvedin 5 mL DME and a solution of 2-vinylpyridine (72 mg) in DME (2 mL) wasadded in one portion, and the stirring was continued for another 4hours. After that, the reaction mixture was concentrated in vacuo toprovide a brown oil from which the product was crystallized by n-pentane(215 mg). 1H-NMR (300 MHz, C₆D₆): δ 1.17 (d, J=6.8 Hz, 6H), 1.27 (d,J=6.8 Hz, 6H), 1.70 (s, 6H), 3.82-3.88 (m, 2H), 5.54 (d, J=7.8 Hz, 1H),5.89 (s, 2H), 6.16-6.23 (m, 1H), 6.60-7.10 (m, 24H), 7.53-7.57 (m, 1H),11.52 (s, 1H).

Example 12: Synthesis of Compound 37. Compound 4 (100 mg) was dissolvedin benzene (1 mL) and the solution of1,1,1,3,3,3-hexafluoro-2-methylpropan-2-ol (18.9 mg) in benzene (1 mL)was added dropwise to the solution at room temperature. After theaddition was completed, the reaction mixture was stirred for 4 hours atthe same temperature, then it was concentrated in vacuo to provide abrown oil from which the product was crystallized by n-pentane (53 mg).1H-NMR (300 MHz, C₆D₆): δ 0.99 (s, 3H), 1.28 (d, J=6.8 Hz, 6H), 1.33 (d,J=6.8 Hz, 6H), 3.20 (s, 3H), 3.84 (m, 2H), 6.18-7.10 (m, 24H), 7.22-7.80(m, 3H), 11.99 (s, 1H).

Example 13: Synthesis Compound 40. To a homogenous solution ofMo(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)(NC₄(CH₃)₂H₂)(4Br-TPPO) (972 mg), which wasreadily prepared in a stoichiometric reaction ofMo(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)-(NC₄(CH₃)₂H₂)₂ precursor and 4Br-TPPOH inanhydrous benzene at ambient temperature, in a 1:1 mixture of anhydrousbenzene and DME (10 mL), 2-vinyloxitetrahydropyrane (138 μL) was added,and the reaction mixture was stirred for an additional 24 hours atambient temperature. Then the volatiles were removed under reducedpressure, and the remaining powdery residue was recrystallized from hotbenzene to obtain brick red micro-crystals (420 mg). 1H-NMR (300 MHz,C₆D₆): δ 0.73 (m, J=11 Hz, 2H), 1.07 (q, J=13 Hz, 1H), 1.27 (m, 1H),1.25 (d, J=7 Hz 6H), 1.28 (d, J=7 Hz 6H), 1.38 (q, 1H), 1.51 (s, 3H),1.78 (d, J=13 Hz, 1H), 2.20 (s, 3H), 2.38 (t, J=12 Hz, 1H), 3.69 (d,J=12 Hz, 1H), 4.21 (sept. J=7 Hz, 2H), 5.00 (dd, J=10, 2 Hz), 5.93 (s,1H), 6.21 (s, 1H), 6.60-7.90 (m, 23H), 11.05 (s, 1H) ppm.

Example 14: Synthesis Compound 41. The potassium salt of 2-ethoxyindole(0.79 g) was added to the solution ofMo(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)(OTf)₂DME (1.50 g) in toluene (15 mL) at−30° C., and the suspension was stirred at room temperature overnight.After completion of the reaction, it was filtered through a Celite padand the filtrate was concentrated to yield an orange solid. The solidprecipitate (150 mg) was dissolved in benzene (3 mL) and the solution of4Br-TPPOH (104 mg) in benzene (3 mL) was added to the reaction mixtureand it was stirred at room temperature for 4 hours, and the volatilematerials were removed under vacuum. The residue was dissolved in 5 mLDME and a solution of 2-vinylbenzene (33 mg) in DME (1 mL) was added inone portion, and the stirring was continued for an additional 4 hours.After that, the reaction mixture was concentrated in vacuo to provide ared oil from which the product was crystallized by n-pentane (145 mg).1H-NMR (300 MHz, C₆D₆): δ 0.86 (t, J=7.1 Hz, 3H), 0.99 (d, J=6.7 Hz,6H), 1.25 (d, J=6.8 Hz, 6H), 3.20-3.80 (m, 7H), 5.28 (s, 1H), 6.30-7.40(m, 31H), 12.55 (s, 1H).

Example 15: Synthesis Compound 50. A solution of Mo(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)(NC₄(CH₃)₂H₂)₂ (200 mg) in benzene (3 mL) was added to asolution of 4Br-TPPOH (161 mg) in benzene (3 mL). The reaction mixturewas stirred at room temperature for 4 hours and the volatile materialswere removed under vacuum. The residue was dissolved in 5 mL DME and asolution of acetic acid ethenyl ester (58 mg) in DME (2 mL) was added inone portion, and the stirring was continued for another 4 hours. Afterthat, the reaction mixture was concentrated in vacuo to provide a brownoil from which the product was crystallized by n-pentane (192 mg).1H-NMR (300 MHz, C₆D₆): δ 1.08 (d, J=6.7 Hz, 6H), 1.19 (d, J=6.6 Hz,6H), 1.73 (s, 6H), 1.79 (s, 3H), 3.70 (m, 2H), 5.95 (s, 2H), 6.70-7.50(m, 23H), 10.61 (s, 1H).

Example 16: Synthesis Compound 55. A solution of Mo(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)(NC₄(CH₃)₂H₂)₂ (200 mg) in benzene (3 mL) was added to asolution of 4Br-TPPOH (161 mg) in benzene (3 mL). The reaction mixturewas stirred at room temperature for 4 hours and the volatile materialswere removed under vacuum. The residue was dissolved in 5 mL DME and asolution of 2-methoxy-4-nitro-1-vinylbenzene (96 mg) in DME (2 mL) wasadded in one portion, and the stirring was continued for another 4hours. After that, the reaction mixture was concentrated in vacuo toprovide a brown oil from which the product was crystallized by n-pentane(293 mg). 1H-NMR (300 MHz, C₆D₆): δ 1.15 (d, J=6.8 Hz, 6H), 1.24 (d,J=6.8 Hz, 6H), 1.43 (s, 6H), 3.27 (s, 3H), 3.65 (m, 2H), 5.74 (d, J=8.4Hz, 1H), 5.86 (s, 2H), 6.50-7.20 (m, 23H), 7.53 (m, 1H), 7.66 (dd,J₁=8.4 Hz, J₂=1.9 Hz, 1H), 12.05 (s, 1H).

Example 17: Synthesis Compound 57. A solution of Mo(N-2,6-i-Pr₂C₆H₃)(CHCMe₂Ph)(NC₄(CH₃)₂H₂)₂ (125 mg) in benzene (2 mL) was added to asolution of 4NO₂-TPPOH (98 mg) in benzene (2 mL). The reaction mixturewas stirred at room temperature for 4 hours and the volatile materialswere removed under vacuum. The residue was dissolved in 2 mL DME and asolution of 2-methoxy-1-vinylbenzene (18 mg) in DME (1 mL) was added inone portion, and the stirring was continued for another 4 hours. Afterthat, the reaction mixture was concentrated in vacuo to provide a brownoil from which the product was crystallized by diethyl ether (81 mg).1H-NMR (300 MHz, C₆D₆): δ 1.18 (d, J=6.8 Hz, 6H), 1.29 (d, J=6.8 Hz,6H), 1.51 (s, 6H), 3.37 (s, 3H), 3.85 (m, 2H), 5.79 (s, 1H), 5.92 (s,1H), 6.04 (m, 1H), 6.43 (m, 1H), 6.60-7.40 (m, 25H), 12.42 (s, 1H).

The other compounds set forth in Table 2, above, were also synthesizedby analogous methods. Each of the compounds was analyzed by 1H NMR.Table 3, below, shows the chemical shift for the alkylidene hydrogen (inppm).

TABLE 3 Compound No. δ for Alkylidene Peak (ppm) 1 12.43 2 11.28 3 11.194 12.44 5 11.12 6 10.99 7 12.01, 11.96 8 11.18 9 11.25 10 10.37, 9.86 11 11.23 12 11.29 13 11.14 14 11.93 15 11.25 16 11.44 17 11.58 18 12.6619 12.80 20 11.26 21 12.51 22 11.77, 11.48 23 12.98 24 13.23, 13.06 2513.05, 12.86 26 12.94 27 11.12 28 11.02 29 11.15 30 11.19 31 11.13 3211.84 33 12.35 34 10.54 35 10.53 36 11.52 37 11.99 38 12.11 39 11.98 4011.05 41 12.55 42 10.16 43 10.30 44 10.35 45 12.12 46 11.05 47 13.33 4812.29 49 11.18 50 10.61 51 10.92 52 10.82 53 11.87 54 10.93 55 12.05 5610.86 57 12.42 58 11.18 59 11.02 60 11.05 61 10.41 62  9.89 63 12.23 6410.95Experimental Details on Metathesis Reaction with Compounds DisclosedHerein

The compounds disclosed above were screened for catalytic activity incertain metathesis reactions. The results are indicated below.

General Procedures for Screening Reactions

For the reaction of oct-1-ene, methyl 9-decenoate, and allylbenzene. Ina nitrogen-filled glovebox, a glass vial was charged with the olefinsubstrate (2.23-2.54 mmol), then a solution of catalyst in benzene(0.025-0.1 M) was added to the vial in one portion and the mixture wasallowed to stir at 22° C. for 15 hours. After that, an aliquot of thereaction was quenched by diethyl ether (100 μL) and the conversion, E/Zselectivity were monitored by GC-MS.

For self-metathesis of diethyl diallylmalonate. In a nitrogen-filledglovebox, a glass vial was charged with diethyl diallylmalonate (0.832mmol) and 1 mL of toluene. A solution of catalyst in benzene (0.025-0.1M) was added to the vial in one portion and the mixture was allowed tostir at 22° C. for 15 hours. After that, an aliquot of the reaction wasquenched by diethyl ether (100 μL) and the conversion was monitored byGC-MS.

GC-MS analytical method for oct-1-ene, methyl 9-decenoate, andallylbenzene. The GC analyses were run using a flame ionization detector(FID). Column: ZB-35HT Inferno (35% Phenyl, 65% Dimethylpolysiloxane)from Phenomenex; 30 m×0.25 mm (i.d.)×0.25 mm film thickness. GC andcolumn conditions: injector temperature of 370° C.; detector temperature240° C.; oven temperature, starting temperature 50° C., hold time 5minutes, ramp rate 25° C./min to 340° C., hold time 12 minutes; carriergas nitrogen.

GC-MS analytical method for diethyl diallylmalonate. The GC analyseswere run using a flame ionization detector (FID). Column: ZB-1 HTInferno (100% Dimethylpolysiloxane) from Phenomenex; 30 m×0.25 mm(i.d.)×0.25 mm film thickness. GC and column conditions: injectortemperature 370° C.; detector temperature 240° C.; oven temperature,starting temperature 50° C., hold time 5 minutes, ramp rate 25° C./minto 340° C., hold time 12 minutes; carrier gas nitrogen.

Compound Activity and Comparison with Known Complexes

Nine complexes, here designated Compounds A to I (below):

were used as comparative examples in the experiments shown below. Thus,in any of the below experimental examples, reference to a compound byletter, e.g., “A”, refers to Compound A, above, and so forth forCompounds B through I.Homo-Metathesis of oct-1-ene.

Comparative compounds A and B were compared with compounds of thepresent disclosure, Compounds 15, 17 and 22, in the homo-metathesis ofoct-1-ene. Table 4 (below) shows the Conversion % at various catalystloadings (in molar ppm). Conversion refers to the percent of thesubstrate (i.e., oct-1-ene) converted to the product (i.e.,E/Z-7-heptene). Conversion %=100−{[(final moles ofreagent)×100]/[initial moles of reagent]}. The catalyst loadings(“Loading”) are calculated relative to the initial concentration of themetathesis substrate.

TABLE 4 Compound Loading (mol ppm) Conversion % A 50 59 B 50 49 15 50 6217 50 69 22 50 83

Homo-Metathesis of Allykbenzene.

Table 5 (below) shows the comparison of catalytic activity for CompoundA and for Compounds 2, 5, 9, and 11 of the present disclosure in thehomo-metathesis of allylbenzene. The loading and the conversionpercentage are calculated as above. The ratio of E isomers formedrelative to Z isomers formed is also determined.

TABLE 5 Compound Loading (mol ppm) Conversion % E/Z ratio A 100 95 37/632 100 90 12/88 5 100 92 19/81 9 100 91 19/81 11  100 92 17/83 A 50 9140/60 2 50 63  5/95 5 50 52  5/95 9 50 63  6/94 11  50 60  5/95

Ring-Closing Metathesis of Diethyl Diallylmalonate.

Table 6 shows the catalytic activity for certain compounds disclosedherein in the ring-closing metathesis of diethyl diallylmalonate.Loading and conversion percentage have the same meanings as above.

TABLE 6 Compound Loading (mol ppm) Conversion % 2 200 93 3 200 65 5 20097 6 200 72 7 200 63 8 200 92 9 200 96 11 200 95 12 200 91 13 200 87 15200 96 16 200 75 17 200 79 22 200 99Cross-Metathesis of Unsaturated Triglyceride with Ethylene.

Table 7 shows the comparison of catalytic activity of Compounds 3 and 4of the present disclosure with that of Compounds D and E (shown below)for the cross-metathesis of food-grade canola oil (triglyceride (“TG”))with ethylene to yield. The canola oil was pre-treated with 6.5 mol %triethylaluminum at 50° C. at 10 atm for 18 hours. The product mixturewas analyzed by gas chromatography with a flame ionization detector(GC-FID) to determine the conversion percentage, the product beingtransesterified with methanol prior to GC-FID analysis. The conversionpercentage was calculated as follows: Conversion %=100−[(final moles ofTG)×100/(initial moles of TG)]. Selectivity was also determined, whichis defined as follows: Selectivity=(moles of methyl9-decenoate)×100/(total moles of all methyl esters in the productmixture except methyl 9-decenoate precursor esters and the saturatedesters coming from canola oil). The yield of methyl 9-decenoate (9DAME)was also calculated, which is defined as: Yield=(moles of9DAME)×100/(initial moles of 9DAME precursor chains in canola oil). InTable 7, the catalyst loadings are given in terms of ppm weight(relative to metathesis substrate). The catalytic activity of compoundsdisclosed herein is compared to Compounds C, D, E, and F.

TABLE 7 Compound Loading (wt ppm) Conversion % Selectivity Yield D 100017 9 9  4 1000 93 50 45 60 1000 97 47 46 36 1000 90 53 45 50 1000 49 5933 C 1000 46 63 24 41 1000 75 67 41 E 250 40 56 23  3 250 56 67 38 351000 80 56 45 40 1000 97 47 46 40 25 27 55 16 F 1000 58 67 39 59 1000 9173 54Homo-Metathesis of methyl 9-decenoate.

Table 8 shows the catalytic activity for certain compounds disclosedherein in the self-metathesis of methyl 9-decenoate. Loading andconversion percentage have the same meanings as in Table 6.

TABLE 8 Compound Loading (mol ppm) Conversion % 35 33 67 36 33 89 40 3392

Thermal Stability of Catalysts—Decomposition Temperature.

Table 9 shows the thermal stability of comparative Compounds G, H, and Iin comparison to compounds of the present disclosure. Thermal stabilitywas determined by dissolving 10 mg of the test samples in 1 mL of1,1,2,2-tetrachloroethane-d₂; the samples were then heated to 60° C.,90° C., and 120° C. and held at that temperature for 1 hour, after whichthe samples were cooled to room temperature and the ¹H-NMR spectrum wasrecorded for each. The decomposition temperature refers to thetemperature at which decomposition of the catalyst was first observed,as measured by a decrease in the intensity of the peak in the ¹H NMRspectrum corresponding to the alkylidene proton.

TABLE 9 Compound Decomposition Temp. (° C.) G 90 41 120 H 60 56 120 I 6058 120

Thermal Stability of Catalysts—Thermal Stability Over Time

Table 10 shows the air stability over time for comparative Compounds A,D, and E in comparison to compounds of the present disclosure. For thisexperiment, a 10-mg sample of the catalyst, in solid crystalline form,was exposed to atmospheric conditions for 30 minutes, 60 minutes, and 24hours. After exposing the sample to atmospheric conditions, the samplewas dissolved in 1 mL of benzene-d₆ and the ¹H NMR spectrum wasrecorded. The percentage decomposition refers to the percentagereduction in the intensity of peak in the ¹H NMR spectrum correspondingto the alkylidene proton in comparison to the intensity of the same peakfor a sample of the same compound that was kept in a glovebox and notexposed to atmospheric conditions. The term “decomposed” refers to 100%decomposition.

TABLE 10 Decomposition Decomposition Decomposition Compound after 30minutes after 60 minutes after 24 hours D 65% decomposed decomposed 4 0%  0% 5% 61  45% 85% decomposed E 85% decomposed decomposed 3 15% 40%decomposed 62  30% 65% decomposed A 90% decomposed decomposed 2 25% 50%decomposed

1. A compound of Formula (II)

wherein: M is a molybdenum atom or a tungsten atom; R¹⁰¹ is phenyl,alkyl, or cycloalkyl, each of which is optionally substituted; R¹⁰² ispyrrolyl or indolyl, each of which is optionally substituted; R¹⁰³ isphenyl, optionally substituted, wherein R¹⁰³ is 2,6-diphenylphenyl or4-bromo-2,3,5,6-tetraphenylphenyl, or wherein R¹⁰³ is:

wherein “iPr” refers to isopropyl, and “OTBDMS” refers totert-butyldimethylsilyloxy; R¹⁰⁴ is a hydrogen atom; R¹⁰⁵ is —O—(C₁₋₆alkyl) or —CH₂—O—(C₁₋₆ alkyl); and R¹⁰⁶ and R¹⁰⁷ are independently ahydrogen atom, C₁₋₆ alkyl, C₁₋₆ alkoxy, or a halogen atom.
 2. Thecompound of claim 1, wherein R¹⁰¹ is phenyl, 2,6-dichlorophenyl,2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-trifluoromethyl phenyl,pentafluorophenyl, tert-butyl, or 1-adamantyl.
 3. The compound of claim1, wherein R¹⁰² is pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl,2,5-diphenylpyrrol-1-yl, or indol-1-yl.
 4. (canceled)
 5. The compound ofclaim 1, wherein R¹⁰⁵ is methyloxy, ethyloxy, or isopropyloxy.
 6. Thecompound of claim 1, wherein R¹⁰⁶ and R¹⁰⁷ are independently a hydrogenatom, methyl, a halogen atom, or methyloxy.
 7. A method for carrying outa metathesis reaction, the method comprising: providing a first compoundhaving one or more carbon-carbon double bonds; and reacting the firstcompound via a metathesis reaction in the presence of a compound ofclaim
 1. 8. The method of claim 7, wherein the first compound has two ormore carbon-carbon double bonds.
 9. The method of claim 8, wherein themetathesis reaction is a ring-closing metathesis reaction between two ofthe two or more carbon-carbon double bonds of the first compound.
 10. Amethod of carrying out a metathesis reaction, the method comprising:providing a first compound having one or more carbon-carbon double bondsand a second compound having one or more carbon-carbon double bonds; andreacting the first compound and the second compound via a metathesisreaction in the presence of a compound of claim
 1. 11. The method ofclaim 10, wherein the first compound and the second compound are thesame compound.
 12. The method of claim 10, wherein the first compoundand the second compound are not the same.
 13. The method of claim 12,wherein the first compound is an internal olefin.
 14. The method ofclaim 13, wherein the second compound is a short-chain alkene.
 15. Themethod of claim 14, wherein the short-chain alkene is ethylene.
 16. Themethod of claim 11 wherein the first compound is an unsaturated ester.17. The method of claim 15, wherein the first compound is an unsaturatedester.
 18. The compound of claim 1, wherein M is a tungsten atom. 19.The compound of claim 1, wherein: M is a tungsten atom; R¹⁰¹ is2,6-dichlorophenyl; R¹⁰² is 2,5-dimethylpyrrol-1-yl; R¹⁰³ is:

wherein “OTBDMS” refers to tert-butyldimethylsilyloxy; R¹⁰⁴ is hydrogen;R¹⁰⁵ is methyloxy; R¹⁰⁶ is hydrogen; and R¹⁰⁷ is hydrogen.
 20. Thecompound of claim 1, comprising a neutral ligand.